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.

Effect of low concentration electrolytes on the formation and corrosion resistance of PEO coatings on AM50 magnesium alloy

In this paper,the formation process,morphology,and electrochemical performance of PEO coatings on AM50 magnesium alloy prepared in low concentration phosphate,aluminate,and phosphate-aluminate electrolytes were systematically studied.The results show that the coatings prepared from the phosphate electrolytes have a higher thickness and better corrosion resistance properties compared to the other electrolytes.The coatings prepared from low concentration phosphate-aluminate mixed electrolytes have slightly thinner thickness,a similar coating structure and an order of magnitude lower value of electrochemical impedance compared with phosphate electrolyte coatings.The Coatings prepared from low concentration aluminate electrolytes have the lowest thickness and the worst corrosion resistance properties which gets close to corrosion behavior of the bare AM50 under the same test conditions.Considering application,coatings prepared from single low concentration phosphate electrolytes and low concentration phosphate-aluminate electrolytes have greater potential than single low concentration aluminate coatings.However,reducing the electrolyte concentrations of coating forming ions too much has negative influence on the coating growth rate.

Effects of Sr and Y on microstructure and corrosion resistance of AZ31 magnesium alloy

The effects of Sr and Y with different contents on the microstructure and corrosion resistance of AZ31 alloy were investigated. The results indicate that the addition of Sr can obviously reduce the grain size of AZ31 alloy and transform β-Mg 17 Al 12 phase from continuous network to scattered form. Simultaneously, Al 4 Sr phase distributed along the boundaries of grains is formed in AZ31-Sr magnesium alloys. The addition of Sr is not as effective as the simultaneous addition of Sr＋Y for the refinement of grains, and Al 2 Y and Al 3 Y phases are distributed both in intracrystalline and along grain boundaries. The corrosion resistance is improved slightly in AZ31 alloy with simultaneous addition of 0.5%Sr＋Y. Due to its smallest corrosion current density and corrosion rate, the corrosion resistance of AZ31-0.5%Sr-1.5%Y magnesium alloy is proved the best.

Electrodeposition of Cu coating with high corrosion resistance on Mg-3.0Nd-0.2Zn-0.4Zr magnesium alloy

To improve the corrosion resistance, electrodeposition of Cu coating on Mg-3.0Nd-0.2Zn-0.4Zr （mass fraction, %NZ30K） magnesium alloy via an appropriate pretreatment was investigated. The surface morphologies, compositions and microstructures of the pretreated films and Cu coating were characterized in detail. The results show that the activation film consists of fluoride and phosphates and Zn immersion film forms preferentially on the eutectic compound Mg12Nd phase region. A smooth, uniform and dense Cu coating is successfully obtained. Potentiodynamic polarization tests reveal that Cu coating can greatly improve the corrosion resistance of NZ30K magnesium alloy. Open circuit potential （OCP） and electrochemical impedance spectroscopy （EIS） tests during long-term immersion further demonstrate that Cu coating can provide an effective protection for NZ30K magnesium alloy from corrosion up to ~60 h, due to its dense structure and a stable passive film formed. In addition, Cu coating exhibits good adhesion to substrate as confirmed by thermal shock test.

Influence of chemical composition on corrosion resistance of AZ91D magnesium alloy ingots

The influence of chemical composition on corrosion resistance of AZ91D magnesium alloys ingots has been investigated. Mass loss method was applied to evaluate the corrosion resistance of AZ91D alloys and the data were analyzed by multiple regression. The results show that the corrosion resistance of this alloy can be improved by increasing Al, Zn and Mn in a certain degree, and will drop with increasing Si and heavy metals (Fe, Cu, Ni). It is found that ingots received from company F should be listed into unusable materials in terms of the corrosion resistance, while among the five suppliers, the only local company E supplied excellent AZ91D magnesium alloy ingots with the best corrosion resistance.

Phosphate film free of chromate, fluoride and nitrite on AZ31 magnesium alloy and its corrosion resistance

A phosphate solution free of chromate, fluoride and nitrite was prepared and an environment-friendly film was obtained on AZ31 magnesium alloy surface via the chemical deposition method. The morphology, composition, phase structure and its corrosion resistance were studied. The effects of film-forming temperature and free acid on corrosion resistance, microstructure and electrochemical behavior of the film were discussed. The results indicate that the corrosion resistance of AZ31 with the phosphate film was better than blank AZ31 substrate, which was most attributed to the great inhibitive action on the anodic dissolution and cathodic hydrogen evolution of the film.

Structure and corrosion resistance of modified micro-arc oxidation coating on AZ31B magnesium alloy

A hydrophobic surface was fabricated on a micro-arc oxidation (MAO) treated AZ31 Mg alloys via surface modification with myristic acid. The effects of modification time on the wettability of the coatings were investigated using the contact angle measuring device. The surface morphologies and structure of the coatings were evaluated using SEM, XRD and FT-IR. The corrosion resistance was investigated by potentiodynamic polarization curves and long-term immersion test. The results showed that the water contact angle (CA) increases gradually with modification time from 0 to 5 h, the highest CA reaches 138° after being modified for 5 h, and the number and size of the micro pores are decreased. The modification method hardly alters crystalline structure of the MAO coating, but improves the corrosion resistance based on the much positive potential and low current density. Moreover, the corrosion resistance and hydrophobicity can be enhanced with increasing the alkyl chain. The wetting and spreading for the alkylcarboxylate with low surface energy become easier on the micro-porous surface, and alkylcarboxylate monolayer will be formed through bidentate bonding, which changes the surface micropores to a sealing or semi-sealing structure and makes the MAO coating dense and hydrophobic. All the results demonstrate that the modification process improves the corrosion protection ability of the MAO coating on AZ31B Mg alloy.

Improvement of wear and corrosion resistance of AZ91 magnesium alloy by applying Ni-SiC nanocomposite coating via pulse electrodeposition

To improve the surface properties of AZ91 magnesium alloy, Ni-SiC nanocomposite coatings with various SiC contents were pulse electrodeposited in modified Watts baths containing SiC nano-particles with the concentration of 0-15 g/L. The morphology of the coatings was studied by scanning electron microscope （SEM）. The SiC content of the coatings was measured by energy dispersive spectroscopy （EDS） analyzer. Microhardness measurement of the coatings showed up to 600% enhancement for the sample produced from the bath with 15 g/L SiC. The corrosion behavior of the coated AZ91 alloy was investigated by potentiodynamic polarization method. The results reveal a significant improvement in the corrosion resistance, that is, the corrosion current density decreases from 0.13 mA/cm2 for uncoated specimen to 1.74x10-6 mA/cm2 for the sample coated from the bath containing 15 g/L SiC and the corrosion potential increases from -1.6 V for uncoated specimen to -0.31 V for the sample coated from the bath. The wear resistance of both coated and uncoated samples was evaluated by pin-on-disc tribotester. The results show that the wear volume loss of coated sample is 8 times less than the bare alloy.

EFFECTS OF Ce ON CORROSION RESISTANCE OF AZ91D MAGNESIUM ALLOY

As-cast and corrosive microstructures of AZ91D alloy containing various Ce contents were observed by optical microscope (OM). The phase compositions of the alloys before and after the corrosion were analyzed by X-ray diffraction (XRD). Meanwhile, the corrosion resistance of the alloys was tested by weight loss and potentiodynamic polarization curve methods respectively. The results show that rod-like Al4Ce phase is formed in AZ91D alloy containing certain Ce content and as-cast microstructures are refined. AZ91D-0.7%Ce alloy has good grain refinement effect. The addition of Ce can reduce the corrosion rate and corrosion current density of AZ91D alloy and those of AZ91D-0.1%Ce alloy reach the minimum, which are 0.35mg/(cm2·d) and 2.761μA/cm2 with 75% and 86% reduction, respectively. The increasing volume fraction and reticular degree of β phase can improve the corrosion resistance of the alloys.

Preparation and corrosion resistance of superhydrophobic coatings on AZ31 magnesium alloy

In order to improve the corrosion resistance of the Mg alloys, the superhydrophobic coatings on AZ31 Mg alloy wereprepared by a two-step process of micro-arc oxidation treatment and superhydrophobic treatment in stearic acid ethanol solution. Theeffects of voltages, frequencies and treatment time on the contact angle of the superhydrophobic treated sample were investigated.The results showed that with increasing the voltage, frequency and treatment time, all of the contact angles of the superhydrophobictreated sample increased first, and then decreased, reaching the maximum values at 350 V, 1000 Hz and 5 min, respectively. Theoptimal superhydrophobic coating was mainly composed of MgO and Mg2SiO4 phases, with the pore diameter of ～900 nm, thethickness of ～6.86 μm and the contact angle of 156.96°. The corrosion current density of the superhydrophobic AZ31 sampledecreased by three orders of magnitude, and the amount of hydrogen evolution decreased by 94.77% compared with that of the AZ31substrate sample.

Effects of Ce addition on microstructure, mechanical properties and corrosion resistance of as-cast AZ80 magnesium alloy

In this study, Ce was introduced into the AZ80 alloy and the effects of Ce addition on the microstructure, mechanical properties and corrosion resistance of the as-cast AZ80 magnesium alloy were investigated. The results show that the addition of Ce into the AZ80 alloy can not only refine the microstructure, but also result in the formation of the needle-like Al4Ce phase. These tiny Al4Ce phases are homogeneously distributed at grain boundaries and within grains. An appropriate Ce addition can also change the β-Mg17Al12 phase at the grain boundaries from continuous network to small island-like. At the same time, with the increase of Ce content from 0 to 2.0wt.%, the macro-hardness of the as-cast alloy is enhanced linearly, while impact toughness, tensile strength and elongation all firstly increase and then decrease. The AZ80 alloy containing 1.0wt.% Ce exhibits the optimal properties. Its macro-hardness, impact toughness, tensile strength and elongation are 61.90 HB, 15.50 J·cm-2, 171.80 MPa and 3.35%, increase by 9.95%, 63%, 13.3% and 36.7%, respectively compared with the base alloy. In addition, Ce can enhance the corrosion resistance of the AZ80 magnesium alloy.

Growth process and corrosion resistance of micro-arc oxidation coating on Mg-Zn-Gd magnesium alloys

A Mg-6Zn-3Gd(mass fraction,%) alloy,noted as ZG63,was coated by different micro-arc oxidation(MAO) processes,and the coating structure and corrosion resistance of the alloy were studied using scanning electron microscopy(SEM),glancing angle X-ray diffractometry(GAXRD) and various electrochemical methods.The micro-arc oxidation process consists of three stages and corresponds with different coating structures.In the initial stage,the coating thickness is linearly increased and is controlled by electrochemical polarization.In the second stage,the coating grows mainly inward and accords with parabolic regularity.In the third stage,the loose coating forms and is controlled by local arc light.The looser coating is mainly composed of MgSiO3 and the compact coating is mainly composed of MgO.From micro-arc oxidation stage to local arc light stage,the corrosion resistance of the coated alloy firstly increases and then decreases.The satisfied corrosion resistance corresponds to the coating time ranging from 6 to10 min.

Microstructure evolution and corrosion resistance of AZ31 magnesium alloy tube by stagger spinning

This study fabricates an AZ31 magnesium alloy tube by spinning technology-power stagger forward spinning.The microstructure evolution of the tube is investigated by combining electron backscatter diffraction and transmission electron microscopy analysis,and the corrosion resistance is measured by an electrochemical corrosion test.Results show that the grains are obviously more uniform and finer along the wall thickness’s direction of the AZ31 alloy tube after the third spinning pass.The number of twins ascends first and then descends,while the varying trend of low-angle grain boundaries(LAGBs)is opposite to that of the twins as the spinning pass increases.With the increase of the total spinning deformation,the deformation texture initially increases and the c-axis of the{0001}crystal plane gradually rotates to the axial direction of the tube;the deformation texture then decreases and the orientation of grains becomes more random.The main mechanism of grain refinement is dynamic recrystallization by the twin-induced way and bowing out of the nucleation at grain boundaries during the first and second pass.However,the dominant mechanism of the refined grain is the high-temperature dynamic recovery in the third pass,and the microstructure mainly consists of substructured grains.After the spinning deformation,the corrosion resistance of the AZ31 alloy tube decreases due to the combined effect of twins and high density-dislocations.

High corrosion resistance of electroless Ni-P with chromium-free conversion pre-treatments on AZ91D magnesium alloy

Phosphate-manganese, tannic acid and vanadium conversion coatings were proposed as an effective pre-treatment layer between electroless Ni-P coating and AZ91D magnesium alloy substrate to replace the traditional chromate plus HF pre-treatment. The electrochemical results show that the chrome-free coatings plus electroless Ni-P coating on the magnesium alloy has the lowest corrosion current density and most positive corrosion potential compared with chromate plus electroless Ni-P coating on the magnesium alloy. These proposed pre-treatment layers on the substrate reduce the corrosion of magnesium during plating process, and reduce the potential difference between the matrix and the second phase. Thus, an electroless Ni-P coating with fine crystalline and dense structure was obtained, with preferential phosphorus content, low porosity, good corrosion-resistance and strengthened adhesion than the chromate plus electroless Ni-P.

Enhanced corrosion resistance of micro-arc oxidation coated magnesium alloy by superhydrophobic Mg-Al layered double hydroxide coating

To further enhance the corrosion resistance of the porous micro-arc oxidation(MAO) ceramic layers on AZ31 magnesium alloy, superhydrophobic Mg-Al layered double hydroxide(LDH) coating was fabricated on MAO-coated AZ31 alloy by using in-situ growth method followed by surface modification with stearic acid. The characteristics of different coatings were investigated by XRD, SEM and EDS. The effect of the hydrothermal treatment time on the formation of the LDH coatings was studied. The results demonstrated that the micro-pores and cracks of MAO coating were gradually sealed via in-situ growing LDH with prolonging hydrothermal treating time. Electrochemical measurement displayed that the lowest corrosion current density, the most positive corrosion potential and the highest impedance modulus were observed for superhydrophobic LDH/MAO coating compared with those of MAO coating and LDH/MAO coating. Immersion experiment proved that the superhydrophobic LDH/MAO coating with the active anti-corrosion capability significantly enhanced the long-term corrosion protection for MAO coated alloy.

Preparation and Corrosion Resistance of Rare Earth Conversion Coatings on AZ91 Magnesium Alloy

The feasibility of forming pollution-free and environmentally benign Ce-based rare earth conversion coatings （short for RECCs） on AZ91 magnesium alloy to enhance corrosion resistance was studied. The effect of optimum processing parameters on corrosion resistance of RECCs, such as density of treating solution, temperature and time of coating formation were discussed. Protective performance of conversion coatings on magnesium alloy was evaluated by moisture/heating test, anodic polarization, etc. The results show that Ce-based RECCs under moisture/heating condition can remain intact, with high coverage and no obvious corrosion phenomenon. Corrosion potential increases and passive phenomenon occurs while current density decreases, therefore Ce-based RECCs can improve corrosion resistance of AZ91 magnesium alloy. The morphology of Ce-based RECCs prepared under optimum process through SEM observation is found to be a few particles coherent to the base coating, and the coating has no cracks and exhibits apparent corrosion resistance during corrosion courses of AZ91 magnesium alloy.

Effect of current density on corrosion resistance of micro-arc oxide coatings on magnesium alloy

Oxide coatings were prepared on magnesium alloys in electrolyte solution of Na2SiO3 at different current densities(3,4 and 5 A/cm 2 )with micro-arc oxidation process.X-ray diffractometry(XRD)results show that the oxide coatings formed on magnesium alloys are mainly composed of MgO and MgAl2O4 phases;in addition,the content of MgO increases with increasing the current density.The morphology and surface roughness of the coatings were characterized by confocal laser scanning microscopy (CLSM).The results show that the surface roughness(Ra)decreases with increasing the current density.Moreover,the electrochemical corrosion results prove that the MgO coating produced in the electrolyte Na2SiO3 at current density of 5 A/cm 2 shows the best corrosion resistance.

Effect of scratch on corrosion resistance of calcium phosphate conversion coated AZ80 magnesium alloy

In order to analyze the effect of scratch on the corrosion behaviour of a calcium phosphate conversion coating(CPCC)on AZ80,the electrochemical testing,scanning vibrating electrode technique(SVET),immersion test and hydrogen evolution experiment were performed to study the corrosion resistance of AZ80,AZ80 with CPCC and coated AZ80 with scratch.The results show that the coating improves the corrosion resistance of the AZ80 from a current density of(85±4)to(4±1)μA/cm^(2).When the coating was damaged,its protection on substrate would be reduced.The scratch with a length of around 12 mm on the coating reduced the corrosion resistance to a current density of(39±1)μA/cm^(2).In addition,the corrosion occurred initially in the scratch area and the corrosion site first occurred at the junction of the scratch and the coating.Besides,the micro corrosion mechanism of the specimen containing scratch was clarified.

Structure and Corrosion Resistance of Microarc Oxidation Coatings on AZ91D Magnesium Alloy

Magnesium alloys are widely used as shells of 3C (computer, mobile phone and consumer electronics) equipments for its impressive mechanical and physical properties, such as low density, good resistance to electromagnetic radiation, suitable for high pressure diecasting and easily recycling, etc. But poor corrosion resistance confines its extensively application. In this paper, protective coatings was successfully prepared on AZ91D magnesium alloys by micro-arc oxidation (MAO) and painting process. Microstructures and phases of MAO coatings were invesgated with scanning electron microscope (SEM) and X-Ray diffractometer. Mechanical properties of MAO coating, such as adhesive force and corrosion resistance, were also tested. Results showed that MAO coatings were a good base for painting process. MAO coatings with paint have good adhesive properties to base metal and excellent corrosion resistance. Micro-arc oxidation with painting process is a good kind of surface treatment to improve the corrosion resistance of mobile phone shell made of AZ91D magnesium alloys.

Microstructure and Corrosion Resistance of Modified AZ31 Magnesium Alloy Using Microarc Oxidation Combined with Electrophoresis Process

A top electrophoresis coating was deposited on the surface microarc oxidation （MAO） modified ceramic coating on AZ31 magnesium alloy. Microstructure and corrosion resistance of this composite coating were studied by SEM, electrochemical potentiodynamic polarization, and acid corrosion test. The results showed that the composite coating with a top electrophoresis coating on the surface of ceramic coating exhibited a better corrosion resistance compared with the coating formed by chemical conversion film combined with electrophoresis process. Corrosive ions could permeate into the substrate with corrosion time, and the composite coating was firstly destroyed around the scratch. The formation of composite coating with a higher adhesive force due to the porosity of the ceramic coating contributed to the improved corrosion resistance property.