Development of high-strength magnesium alloys with excellent ignition-proof performance based on the oxidation and ignition mechanisms: A review

High reactivity and ease of ignition are the major obstacles for the application of Mg alloys in aerospace.Thus,the ignition mechanisms of Mg alloys should be investigated systematically,which can guide the ignition-proof alloy design.This article concludes the factors influencing the ignition resistance of Mg alloys from oxide film and substrate microstructure,and also the mechanisms of alloying elements improving the ignition resistance.The low strength is another reason restricting the development of Mg alloys.Therefore,at the last section,Mg alloys with the combination of high strength and good ignition-proof performance are summarized,including Mg-Al-Ca based alloys,SEN(Mg-Al-Zn-Ca-Y)alloys as well as Mg-Y and Mg-Gd based alloys.Besides,the shortages and the future focus of theses alloys are also reviewed.The aim of this article is to promote the understanding of oxidation and ignition mechanisms of Mg alloys and to provide reference for the development of Mg alloys with high strength and excellent ignition-proof performance at the same time.

Research of growth mechanism of ceramic coatings fabricated by micro-arc oxidation on magnesium alloys at high current mode

Micro-arc oxidation(MAO)coatings of ZK60 magnesium alloys were formed in a self-developed dual electrolyte composed of sodium silicate and phosphate at the high constant current of 1.8 A(15 A/dm^(2)).The MAO process and growth mechanism were investigated by scanning electron microscopy(SEM)coupled with an energy dispersive spectrometer(EDS),confocal laser scanning microscopy and X-ray diffraction(XRD).The results indicate that the growth process of MAO coating mainly goes through“forming→puncturing→rapid growth of micro-arc oxidation→large arc discharge→self-repairing”.The coating grows inward and outward at the same time in the initial stage,but outward growth of the coating is dominant later.Mg,Mg_(2)SiO_(4) and MgO are the main phases of ceramic coating.

Plasma electrolytic oxidation of AZ31 and AZ91 magnesium alloys:Comparison of coatings formation mechanism

The growth kinetics of PEO coatings on AZ31 and AZ91 magnesium alloys were studied and correlated with their structure,compositions(phase and elemental)and corrosion resistance.It was established that the coatings have a two-(outer and anodic)or three-layer structure(outer,inner and anodic)depending on the treatment time.Briefly,at short treatment time only an anodic layer and outer layer exists.Growth of the outer PEO layer takes place due to the micro discharges,which occur in vertical pores and voids with spherical cross-section.If the time is increasing,and electrolyte inside of the pores is heating-up,etching of the Mg substrate and oxide film becomes more dominant and horizontal pores in the interface between coating and metal are formed.In the pores new anodic layer will form and at this time the formation of the third inner layer starts.The growth of the inner layer happens via the anodic film as a result of micro discharge ignition in the horizontal pores,accompanied by formation of plasma in numerous micro-voids of this layer.The coatings formed on AZ91 alloy are denser,than those on AZ31,which is related to the difference in the rates of inner layer growth and dissolving of oxides which are located at the bottom of the horizontal pores.Because of the lower Al content,the AZ31 substrate itself and the also the oxide films are less stable and tend to dissolve at a higher rate compared to AZ91.Thus,it was demonstrated that a good corrosion resistance of the coatings was only obtained on AZ91 and if the average thickness of the coating is around 50μm,correlating with the formation of a sufficiently dense inner laye-Knowing this mechanism,a new two-step treatment was suggested,combining the standard PEO treatment with a subsequent PEO process in an electrolyte supporting the inner film formation.The concept was successfully applied and a further improved corrosion resistance was obtained compared to the single stage PEO process.This improvement of corrosion resistance was related to the better sealing of porosity and formation of a denser inner layer.

Investigation of mutual effects among additives in electrolyte for plasma electrolytic oxidation on magnesium alloys

Plasma electrolytic oxidation(PEO)coatings were prepared on AZ91D magnesium alloys in alkaline silicate-based electrolyte with and without additives.The mutual effects among additives including TiC particles,dispersant polyethylene glycol 6000(PEG6000)and anionic surfactant sodium dodecyl sulfate(SDS)were studied based on orthogonal experiment.The content and distribution of TiC deposited in the coatings were measured by EPMA and EDS.The thicknesses,phase compositions,microstructures and corrosion resistances of the codlings were cAarnined by using TT260 eddy current tuickncss gage,XRD,SEM and clcctrochcniical test,respectively.The results show that the experiment design of this study is the key to study the mutual effects among these additives.Each additive and their interactions all remarkably influence TiC content and corrosion resistance of the coatings.Smaller size TiC is much easier to migrate towards the anode,and the interaction between PEG6000 and SDS both effectively prevents its agglomeration and increases the number of its negative surface charges,which further increase the migration rate and the deposited uniformity of TiC and make TiC have more opportunity to deposit in the discharge channel.Thus,when smaller size TiC,PEG6000 and SDS are all added into the electrolyte,they could improve the anti-corrosion property of the coating to the largest extent attributed to higher TiC content and the densest microstructure of the coating.

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.

Characterization of oxide films formed on magnesium alloys using bipolar pulse microarc oxidation in phosphate solutions

The surface morphology and chemical composition of the oxide films formed on pure magnesium and AZ91D alloy in aqueous electrolytes which contained sodium hexafluorinealuminate（Na3AlF6）, potassium hydroxide （KOH）, sodium hexametahposphate（（NaPO3）6）, and triethanolamine were investigated by X-ray diffraction（XRD）, scanning electron microscope（SEM） and energy dispersive spectroscopy（EDX）. The results show that the input of the negative pulse has great influences on the quantity and the appearance of the microdischarges. Three types of pores can be distinguished on the surface of the oxide film and their size ranges are 0.5-1μm, 1-2μm and 4-7μm, respectively. A few microcracks are seen around the large pores. There exists a remarkable fluoride- enriched zone of about 4-6μm for pure magnesium and 3-5μm for AZ91D alloy at the coating/substrate interface.

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.

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.

A super wear-resistant coating for Mg alloys achieved by plasma electrolytic oxidation and discontinuous deposition

Magnesium alloys are lightweight materials with great potential,and plasma electrolytic oxidation(PEO)is effective surface treatment for necessary improvement of corrosion resistance of magnesium alloys.However,the∼14µm thick and rough PEO protection layer has inferior wear resistance,which limits magnesium alloys as sliding or reciprocating parts,where magnesium alloys have special advantages by their inherent damping and denoising properties and attractive light-weighting.Here a novel super wear-resistant coating for magnesium alloys was achieved,via the discontinuous sealing(DCS)of a 1.3µm thick polytetrafluoroethylene(PTFE)polymer layer with an initial area fraction(A_(f))of 70%on the necessary PEO protection layer by selective spraying,and the wear resistance was exceptionally enhanced by∼5500 times in comparison with the base PEO coating.The initial surface roughness(Sa)under PEO+DCS(1.54µm)was imperfectly 59%higher than that under PEO and conventional continuous sealing(CS).Interestingly,DCS was surprisingly 20 times superior for enhancing wear resistance in contrast to CS.DCS induced nano-cracks that splitted DCS layer into multilayer nano-blocks,and DCS also provided extra space for the movement of nano-blocks,which resulted in rolling friction and nano lubrication.Further,DCS promoted mixed wear of the PTFE polymer layer and the PEO coating,and the PTFE layer(HV:6 Kg·mm^(−2),A_(f):92.2%)and the PEO coating(HV:310 Kg·mm^(−2),A_(f):7.8%)served as the soft matrix and the hard point,respectively.Moreover,the dynamic decrease of Sa by 29%during wear also contributed to the super wear resistance.The strategy of depositing a low-frictional discontinuous layer on a rough and hard layer or matrix also opens a window for achieving super wear-resistant coatings in other materials.

Oxidation behaviour of molten ZK60 and ME20 magnesium alloys with magnesium in 1,1,1,2-tetrafluoroethane/air atmospheres

The oxidation behaviour of molten ZK60 and ME20 magnesium alloys in 1% 1,1,1,2-tetrafluoroethane/air atmospheres at 720 °C was compared with that of molten magnesium. The oxidation kinetics of these three melts was determined by thermograyimetric measuring instrument, and the surface films of the oxidized samples were examined by scanning electron microscope (SEM), X-ray diffractometry (XRD) and X-ray photoelectron spectroscopy (XPS). The results show that the oxidation rate of molten ZK60 or ME20 alloys is much lower than that of molten magnesium in 1% 1,1,1,2-tetrafluoroethane/air atmospheres. The surface film formed on the molten magnesium is composed of MgF2, MgO and C, while the film formed on ZK60 melt mainly consists of MgF2, MgO, C and some ZrF4, and the film on ME20 mainly consists of MgF2, MgO, C and a small amount of CeF4. The good oxidation resistances of ZK60 and ME20 alloy melts may be caused by their major alloying elements Zr and Ce, respectively.

Surface modification of biomedical magnesium alloy wires by micro-arc oxidation

Magnesium alloy wires were processed by micro-arc oxidation （MAO） in a modified silicate-phosphate composite electrolyte containing hydroxyapatite （HA） nanopowders and NaOH. Effects of NaOH content in the composite electrolyte on the microstructure and properties of the MAO ceramic coatings on magnesium alloy wires were studied. It is found that the arc voltage of magnesium alloy wires in the micro-arc oxidation process is significantly reduced while the oxidation rate is accelerated. Addition of 2 g/L NaOH in the composite electrolyte is a better choice for improving corrosion resistance of magnesium alloy wires. During early simulated body fluids （SBF） immersion, the micro-arc oxidized magnesium alloy wires undergo a slow and stable degradation. After soaking for 28 d, the protective ceramic coating still shows no damage but significant degradation is observed for magnesium alloy wires after immersion for more than 60 d.

Corrosion behavior of micro-arc oxidation coating on AZ91D magnesium alloy in NaCl solutions with different concentrations

Ceramic oxide coatings were prepared on AZ91D magnesium alloys in alkaline silicate solution using micro-arc oxidation（MAO） technique.The corrosion behavior of MAO coating on AZ91D magnesium alloys in NaCl solutions with different concentrations（0.1%,0.5%,1.0%,3.5% and 5.0% in mass fraction） was evaluated by electrochemical measurements and immersion tests.The results showed that the corrosion rate of the MAO coated AZ91D increased with increasing chloride ion concentration.The main form of corrosion failure was localized corrosion for the MAO coated AZ91D immersed in higher concentration NaCl solutions（1.0%,3.5% and 5.0%）,while it was general corrosion in dilute NaCl solutions（0.1% and 0.5%）.Two different stages of the failure process of the MAO coated AZ91D could be identified：1） occurrence of the metastable pits and 2） growth of the pits.Different equivalent circuits were also proposed based on the results of electrochemical impedance spectroscopy（EIS） for the MAO coated AZ91D immersed in different concentrations of NaCl solutions for 120 h.

Effect of current frequency on properties of coating formed by microarc oxidation on AZ91D magnesium alloy

The microarc oxidation（MAO） coatings produced at different current frequencies on AZ91 D magnesium alloys were studied systematically. The morphologies, thickness, corrosion performances, and tribological properties of the coatings were investigated by the scanning electron microscopy, the electrochemical measurement system, and MS-T3000 friction test rig, respectively. The results show that the structure of the coatings becomes denser, and thickness becomes thinner with the increase of the current frequency. It is also found that the corrosion resistance of the coatings produced at higher frequency is improved greatly and the difference of the corrosion current density becomes small with increasing current frequency, which is similar to that of the coating thickness. The tribological test shows that the friction coefficient decreases with increasing the current frequency and the wear resistance of the coatings is influenced by both the thickness and structures. All these results were explained by analyzing the growing process of the MAO coating.

Preparation and performance of coating on rare-earth compounds-immersed magnesium alloy by micro-arc oxidation

A composite ceramic coating containing Y2O3-ZrO2-MgO（YSZ-MgO） was prepared on AZ91D magnesium alloy,which was immersed in Y（NO3）3 aqueous solution as pretreatment,by micro-arc oxidation（MAO） process.The morphology,elemental and phase compositions,corrosion behavior and thermal stability of the coatings were studied by SEM,EDX,XRD,electrochemical corrosion test,high temperature oxidation and thermal shock test.The results show that the coating mainly consists of ZrO2,Y2O3,MgO,Mg2SiO4,and MgF2.Among these compounds,Y2O3 accounts for 26.7% of（Y2O3 ＋ ZrO2）.The thickness of YSZ-MgO coating is smaller than that of ZrO2-MgO coating,but its compactness and surface roughness are better than those of ZrO2-MgO coating.YSZ-MgO coating has a good corrosion resistance,and its corrosion rate in 5% NaCl aqueous solution is lower than that of ZrO2-MgO and only about 8.5% of that of AZ91D magnesium alloy.After oxidation at 410 °C,the mass gain of AZ91D magnesium alloy presents a linear increase with the oxidation time.The YSZ-MgO coating and ZrO2-MgO coating can remarkably decrease the oxidation mass gain.The oxidation mass gain of YSZ-MgO coating is lower than that of ZrO2-MgO coating,especially during a long oxidation period.The thermal shock resistance of YSZ-MgO coating is superior to ZrO2-MgO coating.

Characterization of ceramic coating on ZK60 magnesium alloy prepared in a dual electrolyte system by micro-arc oxidation

Micro-arc oxidation （MAO） process was cartied out in an optimized dual electrolyte system to fabricate a compact, smooth, and corrosion resistant coating on ZK60 Mg alloy. The microstructural characteristics of coating were investigated by scanning electron microscopy （SEM） coupled with an energy dispersive spectrometer （EDS） and X-ray diffraction （XRD）. Test of mass loss was conducted at a 3.5 % NaCl solution to assess the resistance to corrosion. The bonding strength between the coating and ZK60 substrate was evaluated using scratch experiment. The results reveal that MgA1204 and MgO are the main phases of ceramic coating obtained in the dual electrolyte system. The corrosion rate of coating prepared in the optimized dual electrolyte is only 0.0061 g.m-2.h-1, which demonstrates excellent corrosion resistance. This is mainly due to the compact, uniform coating with high bonding strength.

The effect of pulse frequency on the electrochemical properties of micro arc oxidation coatings formed on magnesium alloy

Micro arc oxidation(MAO)coatings were formed on magnesium alloy AZ31B to improve the corrosion resistance using environmental friendly electrolyte solution under single-polar pulse power supply.The effect of electrical parameters of pulse frequency on the coating performance was studied at frequencies of 2.5 Hz,25 Hz and 250 Hz.The coating performance at different frequencies was characterized by scanning electron microscopy(SEM),energy-dispersive X-ray spectroscopy(EDS)and potentiodynamic polarization testing method.It was found that the corrosion resistance of the MAO coatings was improved when increasing the pulse frequencies from 2.5 Hz to 250 Hz.The corrosion current in 250 Hz case decreased by three orders of magnitude as compared with bare Mg alloy and the corrosion impedance also increased remarkably,means significantly enhanced corrosion resistance than bare Mg alloy.The results give us more insight in the optimization of electrical parameters to improve the MAO coating performance.The MAO technology is attractive for application on magnesium and other light alloys for surface protection in automotive and space industries.

Corrosion resistance and mechanisms of smart micro-arc oxidation/epoxy resin coatings on AZ31 Mg alloy: Strategic positioning of nanocontainers

Smart micro-arc oxidation(MAO)/epoxy resin(EP) composite coatings were formed on AZ31 magnesium(Mg) alloy. Mesoporous silica nanocontainers(MSN) encapsulated with sodium benzoate(SB) corrosion inhibitors were strategically incorporated in the MAO micropores and in the top EP layer. The influence of the strategic positioning of the nanocontainers on the corrosion protective performance of coating was investigated. The experimental results and analysis indicated that the superior corrosion resistance of the hybrid coating is ascribed to the protection mechanisms of the nanocontainers. This involves two phenomena:(1) the presence of the nanocontainers in the MAO micropores decreased the distance between MSN@SB and the substrate, demonstrating a low admittance value(^5.18 × 10^(-8)Ω^(-1)), and thus exhibiting significant corrosion inhibition and self-healing function;and(2) the addition of nanocontainers in the top EP layer densified the coating via sealing of the inherent defects, and hence the coating maintained higher resistance even after 90 days of immersion(1.13 × 10^(10)Ω cm^(2)).However, the possibility of corrosion inhibitors located away from the substrate transport to the substrate is reduced, reducing its effective utilization rate. This work demonstrates the importance of the positioning of nanocontainers in the coating for enhanced corrosion resistance,and thereby providing a novel perspective for the design of smart protective coatings through regulating the distribution of nanocontainers in the coatings.

Improving the corrosion properties of magnesium AZ31 alloy GTA weld metal using microarc oxidation process

In this work, the morphology, phase composition, and corrosion properties of microarc oxidized (MAO) gas tungsten arc (GTA) weldments of AZ31 alloy were investigated. Autogenous gas tungsten arc welds were made as full penetration bead-on-plate welding under the alternating-current mode. A uniform oxide layer was developed on the surface of the specimens with MAO treatment in silicate-based alkaline electrolytes for different oxidation times. The corrosion behavior of the samples was evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy. The oxide film improved the corrosion resistance substantially compared to the uncoated specimens. The sample coated for 10 min exhibited better corrosion properties. The corrosion resistance of the coatings was concluded to strongly depend on the morphology, whereas the phase composition and thickness were concluded to only slightly affect the corrosion resistance.

Effect of magnesium in aluminum alloys on characteristics of microarc oxidation coatings

Microarc oxidation(MAO) coatings were prepared on the surface of aluminum alloys with different contents of magnesium. The morphologies and surface roughness of the coatings were characterized by Confocal laser scanning microscopy(CLSM). Phase and chemical composition of the MAO coatings were analyzed by X-ray diffractometry(XRD) and X-ray photoelectron spectroscopy(XPS). The experimental results show that the coatings formed on different substrates have two-layer morphologies and are mainly composed of Al2O3 and Al-Si-O phases. In addition, the content of Al2O3 increases with increasing the content of magnesium. XPS results prove that magnesium from substrate indeed participates in the MAO process and is incorporated into the coating in the form of MgO. The coating formed on Al-3Mg substrate has the smallest mass loss and the lowest friction coefficient of 0.17-0.19.

Effects of rare earths on the microarc oxidation of a magnesium alloy

The effects of rare earths on the properties of the microarc oxidation（MAO） coating on a magnesium alloy were investigated by means of scanning electron microscopy（SEM）,energy dispersive X-ray spectroscopy（EDS）,and electrochemistry methods.The results show that a nice and compact MAO coating was successfully obtained when the magnesium alloy was treated in nitrate solutions as the pre-treatment of MAO.However,the MAO was not successfully completed for the silicate electrolytes with the addition of rare earths.After the magnesium alloy being treated by rare earth nitrate,the obtained MAO coating has advantages such as uniform distribution of thickness,improved corrosion resistance,and nice-uniform surface,as compared with the untreated magnesium alloy.In addition,the time of non-ESP,the voltage and current density of the MAO process obviously decrease.Cerium oxide doped on the surface of the magnesium alloy can significantly improve the corrosion resistance of the MAO coating and decrease the current density of the MAO process,as compared with lanthanum oxide,whereas the doped rare earths have no significant effect on the components of the MAO coating.