Influence of laser parameters on the microstructures and surface properties in laser surface modification of biomedical magnesium alloys

Biodegradable implants from magnesium(Mg)alloys have emerged in the biomedical field especially in the orthopedic and cardiovascular stent applications owing to their low density,high specific strength,excellent machinability,good biocompatibility,and biodegradability.The primary shortcoming of Mg-based implants is their low corrosion resistance in the physiological environment,which results in premature mechanical integrity loss before adequate healing and the production of excessive hydrogen gas,which is harmful to the body tissues and negatively affects the biocompatibility of the implant.Laser surface modification has recently received attention because it can improve the surface properties such as surface chemistry,roughness,topography,corrosion resistance,wear resistance,hydrophilicity,and thus cell response to the surface of the material.The composition and microstructures including textures and phases of laser-treated surfaces depend largely on the laser processing parameters(input laser power,laser scan velocity,frequency,pulse duration,pressure,gas circulation,working time,spot size,beam focal position,and laser track overlap)and the thermophysical properties of the substrate(solubility,melting point,and boiling point).This review investigates the impacts of various laser surface modification techniques including laser surface melting,laser surface alloying,laser cladding,laser surface texturing,and laser shock peening,and highlights their significance in improving the surface properties of biodegradable Mg alloys for implant applications.Additionally,we explore how different laser process parameters affect its composition,microstructure,and surface properties in each laser surface modification technique.

Structure and effects of electroless Ni-Sn-P transition layer during acid electroless plating on magnesium alloys

An electroless ternary Ni-Sn-P transition layer with high corrosion resistance was applied for acid electroless nickel plating on magnesium alloys. The surface morphologies and microstructure of the traditional alkaline electroless Ni-P and novel Ni-Sn-P transition layers were compared by SEM and XRD, and the bonding strengths between the transition layers and AZ31 magnesium alloys were tested. The corrosion resistance of the samples was analyzed by porosity test, potentiodynamic polarization, electrochemical impedance spectroscopy（EIS） in acid electroless solution at p H 4.5 and immersion test in 10% HCl. The results indicate that the transition layer is essential for acid electroless plating Ni-P coatings on magnesium alloys. Under the same thin thickness（-6 μm）, the electroless Ni-Sn-P transition layer possesses superior properties to the traditional Ni-P transition layer, including high amorphization, smooth and dense surface without pores, enhanced bonding strength and corrosion resistance. Most importantly, acid electroless Ni-P coatings can be successfully deposited on magnesium alloys by using Ni-Sn-P transition layer.

Research progress in friction stir processing of magnesium alloys and their metal matrix surface composites: Evolution in the 21^(st )century

Rising concerns about climate change drive the demand for lightweight components.Magnesium(Mg)alloys are highly valued for their low weight,making them increasingly important in various industries.Researchers focusing on enhancing the characteristics of Mg alloys and developing their Metal Matrix Composites(MMCs)have gained significant attention worldwide over the past decade,driven by the global shift towards lightweight materials.Friction Stir Processing(FSP)has emerged as a promising technique to enhance the properties of Mg alloys and produce Mg-MMCs.Initially,FSP adapted to refine grain size from the micro to the nano level and accelerated the development of MMCs due to its solid-state nature and the synergistic effects of microstructure refinement and reinforcement,improving strength,hardness,ductility,wear resistance,corrosion resistance,and fatigue strength.However,producing defect-free and sound FSPed Mg and Mg-MMCs requires addressing several variables and their interdependencies,which opens up a broad range of practical applications.Despite existing reviews on individual FSP of Mg,its alloys,and MMCs,an attempt has been made to analyze the latest research on these three aspects collectively to enhance the understanding,application,and effectiveness of FSP for Mg and its derivatives.This review article discusses the literature,classifies the importance of Mg alloys,provides a historical background,and explores developments and potential applications of FSPed Mg alloys.It focuses on novel fabrication methods,reinforcement strategies,machine and tool design parameters,material characterization,and integration with other methods for enhanced properties.The influence of process parameters and the emergence of defects are examined,along with specific applications in mono and hybrid composites and their microstructure evolution.The study identifies promising reinforcement materials and highlights research gaps in FSP for Mg alloys and MMCs production.It concludes with significant recommendations for further exploration,reflecting ongoing advancements in this field.

A review on developing high-performance ZE41 magnesium alloy by using bulk deformation and surface modification methods

Magnesium(Mg)alloys are generally used in light-weight structural applications due to their higher specific strength.However,the usage of these Mg alloys is limited due to their poor formability at room temperature,which is attributed to lower count of slip systems associated with the hcp crystal structure.To address these limitations,several new magnesium alloys and also many processing strategies have been developed and reported in the literature.ZE41 Mg is an alloy with significant quantities of zinc(Zn)and rare earth(RE)elements and has emerged as a promising material for aerospace,automotive,electronics,biomedical and many other industries.To make this alloy more competitive and viable,it should possess better mechanical and corrosion properties.Hence,the current paper reviews the effect of bulk mechanical processing on grain refinement,microstructural modification,and corresponding changes in the mechanical behaviour of ZE41Mg alloy.Further,the effect of various surface modification techniques on altering the surface microstructure and surface properties such as wear and corrosion are also briefly summarized and presented.This review also discusses the challenges and the future perspectives in developing high-performing ZE41 Mg alloys.

Electroplating zinc transition layer for electroless nickel plating on AM60 magnesium alloys

Electroplating zinc coating as transition layer of electroless nickel plating on AM60 magnesium alloys was investigated. The zinc film can be deposited in a pyrophosphate bath at 50-60℃under current density of 0.5-1.5 A/dm2. A new fore treatment technology was applied by acid cleaning with a solution containing molybdate and phosphorous acid, by alkaline cleaning in a bath containing molybdate and sodium hydroxide. The subsequent electroless plating was carried out in nickel sulfate bath. The SEM observation shows that the deposition is uniform and compact. The polarization curve measurements show that the corrosion potential of the zinc plating in 3.5% NaCl is about -1.3 V(vs SCE) which is noble than that of magnesium substrate. The zinc electroplating can be applied as the pretreatment process for electroless nickel plating on magnesium alloys.

Properties of fluoride film and its effect on electroless nickel deposition on magnesium alloys

The physical characteristics and microstructure of the fluoride film formed during activation were investigated using SEM,XPS and SAM,and its stability in electroless nickel(EN) bath was analyzed.The effects of the fluoride film on EN deposition were studied additionally.The results show that the fluoride film on magnesium alloys is a kind of porous film composed of MgF2 with thickness of 1.6-3.2 μm.The composition of the activation bath and pretreatment of EN processing have influence on the composition of the fluoride film.The fluoride is stable and dissolves little in EN bath;as a result,the fluoride film can protect magnesium substrate from the corrosion of EN bath.The composition of fluoride determines the initial deposition of EN and part of the fluoride film finally exists as inclusion in EN coating.

Effect of initial deposition behavior on properties of electroless Ni-P coating on ZK60 and ME20 magnesium alloys

The composition of magnesium alloys is greatly associated with initial deposition behavior of electroless Ni-P coatings.Thus,the initial deposition behavior of electroless Ni–P coatings on ZK60 and ME20 alloys was investigated.The results indicated that differences in the alloy compositions significantly influenced the initial deposition process and the adhesive strength,corrosion resistance,and crystal structure.The initial deposition of coatings on ZK60 and ME20 alloys preferentially occurred on the precipitates.The precipitates in ZK60 alloy had higher chemical activity after HF activation and controlled the initial deposition rate of the coating.The initial deposition rate of the coating on ME20 alloy mainly depended on the density of the Mg F2 film formed by HF activation rather than on the precipitates.Owing to differences in the initial deposition process,the coating on ZK60 alloy had higher adhesive strength and better corrosion resistance than that on ME20 alloy.The coatings on ZK60 and ME20 alloys mainly had crystalline structures,and the coating on ME20 alloy had also a slight microcrystalline structure.

Progress of electroplating and electroless plating on magnesium alloy

The current research processes of electroplating and electroless Ni-P alloy plating on magnesium alloys were reviewed. Theoretically,the reason for difficulties in electroplating and electroless plating on magnesium alloys was given.The zinc immersion, copper immersion,direct electroless Ni-P alloy plating and electroplating and electroless plating on magnesium alloys prepared by chemical conversion coating were presented in detail.Especially,the research development of magnesium alloy AZ91 and AZ31 was discussed briefly.Based on the analysis,the existing problems and future research directions were then given.

Electrochemical behavior of Cu-Zn-Al shape memory alloy after surface modification by electroless plated Ni-P

The electrochemical behavior of Cu-Zn-Al shape memory alloy (SMA) with andwithout electroless plated Ni-P was investigated by electrochemical methods, in artificial Tyrode'ssolution. The results showed that Cu-Zn-Al SMA engendered dezincification corrosion in Tyrode'ssolution. The anodic active current densities as well as electrochemical dissolution sensitivity ofthe electroless plated Ni-P Cu-Zn-Al SMA increased with NaCl concentration rising, pH of solutiondecreasing and environmental temperature uprising. X-ray diffraction analysis indicated that aftersurface modification by electroless plated Ni-P, an amorphous plated film formed on the surface ofCu-Zn-Al SMA. This film can effectively isolate matrix metal from corrosion media and significantlyimprove the electrochemical property of Cu-Zn-Al SMA in artificial Tyrode's solution.

Homogenization pretreatment and electroless Ni-P plating on AZ91D magnesium alloy

Electroless nickel plating on AZ91D substrate with a new and eco-friendly pretreatment process based on tuning an electrochemical homogeneous surface was investigated. The morphology, deposition process, chemical composition and microstructure of Ni-P coating were studied. It is indicated that β phases are selectively removed, producing a microstructural homogeneous surface and the subsequent uniform and compact Zn immersion layer. A defect-free and well adhesive Ni-P coating can be successfully obtained due to its uniform nucleation and growth based on such pretreatment. Potentiodynamic polarization and electrochemical impedance spectroscopy （EIS） tests reveal that Ni-P coating could significantly improve the corrosion resistance of AZ91D substrate.

Recent advances in surface endothelialization of the magnesium alloy stent materials

Magnesium and its alloy have good mechanical properties and biodegradability,and have become the hotspot of the next-generation biodegradable vascular stent materials.However,their rapid degradation in vivo and poor biocompatibility are still the bottlenecks of clinical applications for the cardiovascular stents.In particular,how to induce the repair and regeneration of the vascular endothelial with normal physiological functions on the surface of the magnesium alloy stent materials represents the key to its clinical application in the field of cardiovascular stents.It has been believed that it is an ideal way to completely solve the postoperative complications through constructing the multifunctional anti-corrosive bioactive coating on the magnesium alloy surface to induce the formation of vascular endothelium with normal physiological functions.However,how to construct a corrosion-resistant multifunctional bioactive coating with the good endothelial regeneration abilities on the magnesium alloy surface still faces a great challenge.This paper mainly focused on highlighting and summarizing the recent advances in the surface endothelialization of the magnesium alloy materials for the vascular stent,including the bio-inert coating,in-situ immobilization of bioactive molecules on the surface,polymer coating loaded with bioactive factors,novel multifunctional polymer coating,bioactive micropatterns,bioactive layer with glycocalyx-like structure,NO-releasing coating and bioactive sol-gel coating.The advantages and disadvantages of these strategies were discussed and analyzed.Finally,in the senses of future development and clinical application,this paper analyzed and summarized the development direction and prospect of surface endothelialization of the magnesium alloy vascular stents.It is anticipated that this review can give the new cues to the surface endothelialization of the cardiovascular magnesium alloy stents and promote future advancements in this field.

Electroless nickel fabrication on surface modified magnesium substrates

In recent years,magnesium(Mg)has evolved as a salient material,in affiliation with electroless nickel(Ni)coating,which have found applications in automobiles,aerospace and confederate fields attributing to its excellent inherent weight sensitive properties.However,being acknowledged for its remarkable auxiliary properties like flexible machining,appreciable weight sensitivity and ability to be patently diecast into mesh constructs,magnesium is prejudiced by aeronautical standards predominantly for its inferior corrosion resistance properties.In this sense,electroless nickel plating on magnesium and its alloys has been suggested to extricate it from corrosion problem and make it more competitive in industrial and defence applications.Autocatalytic fixation of metal ions onto respective substrates accrues and alters their mechanical,electrochemical and tribological properties,destitute of any electric current aid.This proficiently identified technique is prosecuted with the assistance of a series of sequenced operations involving a prior pretreatment,which corresponds to the chemical cleaning of the substrate surface;electroless coating;and a later activation process which is a mild etching of the electroless coated surface.The susceptibility of magnesium to this methodology has advanced and propagated its exercise and applicability in aircraft,satellites and allied aeronautical fields.Contemporarily,researchers have proposed various eco-friendly and modified duplex and composite coatings which have transmuted properties of these appendages by tailoring alloy compositions and reagents employed.This review article systematically colligates various considerations and evaluations on electroless nickel applications of magnesium and its alloys and explicates how it anchors its practice in the respective domains.Furthermore,a comprehensive analysis is devised based on the pre-existing treatment methods for accomplishing the same.

Influence of pH values on electroless Ni-P-SiC plating on AZ91D magnesium alloy

A novel Ni-P-SiC composite coating was prepared by electroless plating in order to improve the corrosion capacity and wear resistance of AZ91D magnesium alloy.The influence of pH values on deposition rates and properties of the coatings was studied.The microstructure and phase structure of the Ni-P-SiC coatings were analyzed by scanning electron microscopy(SEM)and X-ray diffractometry(XRD).The corrosion and wear resistance performances of the coatings were also investigated through electrochemical technique and pin-on-disk tribometer,respectively.The results indicate that the composite coating is composed of Ni, P and SiC.It exhibits an amorphous structure and good adhesion to the substrate.The coatings have higher open circuit potential than that of the substrate.The composite coating obtained at pH value of 5.2 possesses optimal integrated properties,which shows similar corrosion resistance and ascendant wear resistance properties to the substrate.

Microstructure and electrical conductivity of electroless copper plating layer on magnesium alloy micro-arc oxidation coating

In order to impart electrical conductivity to the magnesium alloy micro-arc oxidation(MAO)coating,the electroless copper plating was performed.Effects of plating temperature and complexing agent concentration on the properties of the electroless copper plating layers were studied by measuring their microstructure,corrosion resistance and electrical conductivity.It was found that the optimized plating temperature was 60°C,and the most suitable value of the complexing agent concentration was 30 g/L.Under this condition,a complete and dense plating layer could be obtained.The formation mechanism of the plating layer on magnesium alloy MAO coating was analyzed.A three-stage model of the plating process was proposed.The square resistance of the plated specimen was finally reduced to 0.03Ω/□after the third stage.Through electroless copper plating,the MAO coated sample obtained excellent electrical conductivity without significantly reducing its corrosion resistance.

Effect of multifunction cavitation using phosphoric acid on fatigue and surface properties of AZ31 magnesium alloy

Magnesium alloy is attractive for lightweight construction but often suffers from poor corrosion resistance and low strength.Cavitation processing with chemicals,i.e.,multifunction cavitation(MFC),was introduced to form a high-corrosion film and improve the fatigue properties of an AZ31 magnesium alloy.Surface analysis and plane bending fatigue tests were conducted for the MFC-treated magnesium alloy at a stress ratio,R,of-1.The mechanical action of cavitation bubbles improved the fatigue life of magnesium alloys due to increasing the surface hardness and generating compressive residual stress.However,the combined mechanical and electrochemical action during MFC formed pits on the surface.These pits were large enough to easily nucleate an initial fatigue crack.In addition,the magnesium alloys without pit formation,for which a coating process using phosphoric acid was conducted after MFC using water,showed superior fatigue properties.

Corrosion and wear properties of electroless Ni-P plating layer on AZ91D magnesium alloy

A direct electroless Ni-P plating treatment was applied to AZ91D magnesium alloy for improving its corrosion resistance and wear resistance. Corrosion resistance of the Ni-P coatings was evaluated by potentiodynamic polarization and immersing experiments in 3.5% NaCl solution. The wear resistance of the coatings was investigated by the wear track and the mass change after ball-on-disk experiment. The results show that corrosion resistance and wear resistance of the AZ91D alloy are greatly improved after direct electroless Ni-P plating. No discoloration is noticed until 4 d of immersion in 3.5% NaCl solution. Potentiodynamic polarization experiments show that the free corrosion potential of magnesium alloy is shifted from -1 500 mV to -250 mV and passivation occurs at 1 350 mV after direct electroless plating. The friction coefficients and wear rates of Ni-P coating and Ni-P coating after tempering are 0.10-0.351, 9.038×10-3 mm3/m and 0.13-0.177, 3.056×10-4 mm3/m, respectively, at a load of 1.5 N with dry sliding. Although minor hurt on corrosion resistance was caused, significant improvement of wear resistance was obtained after tempering treatment of the coating.

Direct electroless Ni-P plating on AZ91D magnesium alloy

An electroless Ni-P plating treatment was applied on AZ91D magnesium alloy to improve its corrosion resistance. Optimum pretreatment conditions and optimum bath of electroless nickel plating for magnesium alloy were found through many experiments. In order to avoid bother of pre-plating medium layer, a set of procedure of direct electroless Ni-P under the acid condition was investigated. The properties of the coating with 10% phosphorus were investigated. The results show that a coating with high hardness, low porosity and good adhesive strength is obtained. X-ray diffraction patterns show that the structure of the coating is an amorphous phase. After annealing at 400℃, the amorphous phase of Ni-P is transformed to crystalline phases, and some intermetallics as Ni3P and Ni5P2 are deposited from Ni-P solid solution along with an enhancing hardness from Hv 450 to Hv 910.

Electroless nickel-plating on die cast magnesium alloy AZ91D

Electroless nickel-plating on die cast magnesium alloy AZ91D was investigated. Growth of the electroless nickel-plating coating was characterized using scanning electron microscopy. Corrosion resistance of the coating was evaluated by open circuit potential and potentiodynamic polarization curves in 3.5%(mass fraction) NaCl solution. The results show that plating deposition is initiated on the crevices and then spread onto primary α phase. The corrosion potentials for die cast magnesium alloy AZ91D and nickel-plating coating are about -1.45 V and -0.36 V(vs. SCE),respectively. No discoloration,cracks,blisters,or peeling appear by heat-quench test. The results show that the corrosion potential of Ni-P coating is increased by 1 000 mV and corrosion resistance for die cast magnesium alloy AZ91D is improved. The adhesion between the coating and the substrate is excellent. Electroless nickel plating is a promising method to enhance magnesium alloys resistance for attacking.

Pretreatment-free Ni-P plating on magnesium alloy at low temperatures

Electrochemically promoted electroless plating(EPEP)was used for the application of pretreatment-free Ni-P coating on AM60B magnesium alloy at low temperatures and the obtained coating was characterized by SEM,AFM,EDS and XRD techniques.Compact,uniform,and medium-phosphorus Ni-P coating with mixed crystalline-amorphous microstructure was obtained by applying a cathodic current density of4mA/cm^2at50℃.Also,island-like nickel clusters were deposited on the alloy surface under the same plating condition but without applying the cathodic current.In addition,the durability of the magnesium alloy against corrosion was strongly improved after plating via EPEP technique which was revealed by electrochemical examinations in3.5%NaCl(mass fraction)corrosive electrolyte.The results of the electrochemical examinations were confirmed by microscopic observations.Thickness,microhardness,porosity and adhesive strength of the deposits were also qualified.

Advances in coatings on magnesium alloys for cardiovascular stents-A review

Magnesium(Mg)and its alloys,as potential biodegradable materials,have drawn wide attention in the cardiovascular stent field because of their appropriate mechanical properties and biocompatibility.Nevertheless,the occurrence of thrombosis,inflammation,and restenosis of implanted Mg alloy stents caused by their poor corrosion resistance and insufficient endothelialization restrains their anticipated clinical applications.Numerous surface treatment tactics have mainly striven to modify the Mg alloy for inhibiting its degradation rate and enduing it with biological functionality.This review focuses on highlighting and summarizing the latest research progress in functionalized coatings on Mg alloys for cardiovascular stents over the last decade,regarding preparation strategies for metal oxide,metal hydroxide,inorganic nonmetallic,polymer,and their composite coatings;and the performance of these strategies in regulating degradation behavior and biofunction.Potential research direction is also concisely discussed to help guide biological functionalized strategies and inspire further innovations.It is hoped that this review can give assistance to the surface modification of cardiovascular Mg-based stents and promote future advancements in this emerging research field.