Analyses of Microarc Oxidation Coating Formed on AZ91D Alloy in Phosphate Electrolytes

This paper studied the appearance transition of microdischarges, the phase composition and the morphology evolution of the oxide film formed by microarc oxidation on AZ91D magnesium alloy. The appearance of microdischarges population experienced apparent changes in size, spatial density and color, which was related with the changes of the type and quantity of the disintegrated gas bubbles generated at the interface between the electrolyte and substrate. Correspondingly, the diameter of micropores together with net-like fine microcracks increased when a higher voltage was employed. The coating was composed of MgO, MgAl2O4 and there existed a fluoride-enriched zone of about 3-5μm at the film/substrate interface.

MICROSTRUCTURAL FORMATION MECHANISM OF SEMI-SOLID AZ91D ALLOY

With the help of an electromagnetic stirring device and alloy melt quenching technology, the microstntcture of semi-solid AZqlD magnesium alloy slurry stirred by a rotationally electromagnetic fieM was studied and the experimental results are shown as the following. The primary α-Mg grains are refined obviously when the slurry is stirred by a rotational electromagnetic field during continuously cooling and they are eventually changed to fine rosette grains or spherical grains. If the above semi-solid slurty is further stirred isothermally for some time, much more spherical primary α-Mg grains can be obtained. If the melt is first cooled down to a given semi-solid temperature and then starts being stirred by the rotational electromagnetic field, the primary α-Mg dendrites will be large, and a longer time will be taken and a larger stirring power will be needed for the secondary army of the dendrites to be remelted on the roots to prepare an ideal semiolid slurry. Theoretical analysis indicates that the strong flow motion leads to a more even temperature field and a solute field and stronger man-made temperature fluctuation in the AZglD magnesium alloy melt so that the spherical primary α-Mg grains are increased in the slurry. Moreover, all the measures promoting the temperature fluctuation will be favorable to the formation of spherical primary α-Mg grains and all the factors increasing the arm＇s root remelting difficulty will be favorable to the formation of rosette-type primary α-Mg grains.

Microstructural formation of semi-solid AZ91D alloy stirred by electromagnetic field

With the help of an electromagnetic stirring device, alloy melt quenching and EBSD （electron back scatter diffraction） analysis technology, the microstructure of the semi-solid AZ91D magnesium alloy slurry stirred by rotational electromagnetic field under different stirring power conditions has been studied. The results show that the size of primary α-Mg phase is reduced obviously when the solidifying alloy melt is stirred by rotational electromagnetic field, moreover, the primary α-Mg grains are changed to fine rosette grains or spherical grains which are proved to belong to the different grains in three-dimension by the EBSD analysis technology. The results also show that the stirring power is an important processing parameter in the preparation of the semi-solid AZ91D magnesium alloy slurry. The larger the stirring power, the finer the primary α-Mg grains, the less the rosette primary α-Mg grains, and the more the spherical primary α-Mg grains. Theoretical analysis indicates that a stronger flow motion leads to a more even temperature field and solute field and a stronger man-made temperature fluctuation in the alloy melt so that the specially fine rosette and/or spherical primary α-Mg grains are formed in the semi-solid AZ91D magnesium alloy slurry.

Mechanism of microarc oxidation on AZ91D Mg alloy induced byβ-Mg_(17)Al_(12) phase

This work proposed a strategy of indirectly inducing uniform microarc discharge by controlling the content and distribution ofβ-Mg_(17)Al_(12)phase in AZ91D Mg alloy.Two kinds of nano-particles(ZrO_(2)and TiO_(2))were designed to be added into the substrate of Mg alloy by friction stir processing(FSP).Then,Mg alloy sample designed with different precipitated morphology ofβ-Mg_(17)Al_(12)phase was treated by microarc oxidation(MAO)in Na_(3)PO_(4)/Na2SiO3electrolyte.The characteristics and performance of the MAO coating was analyzed using scanning electron microscopy(SEM),energy dispersive spectrometer(EDS),X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),contact angle meter,and potentiodynamic polarization.It was found that the coarseα-Mg grains in extruded AZ91D Mg alloy were refined by FSP,and theβ-Mg_(17)Al_(12)phase with reticular structure was broken and dispersed.The nano-ZrO_(2)particles were pinned at the grain boundary by FSP,which refined theα-Mg grain and promoted the precipitation ofβ-Mg_(17)Al_(12)phase in grains.It effectively inhibited the“cascade”phenomenon of microarcs,which induced the uniform distribution of discharge pores.The MAO coating on Zr-FSP sample had good wettability and corrosion resistance.However,TiO_(2)particles were hardly detected in the coating on TiFSP sample.

Corrosion protection of AZ91D magnesium alloy by a cerium-molybdenum coating-The effect of citric acid as an additive

In order to improve the corrosion resistance of AZ91D magnesium alloy,a coating was formed by a potentiostatic technique from a solutions containing Ce(NO_(3))_(3),Na_(2)MoO_(4)and citric acid(H_(3)Cit).The degree of corrosion protection achieved was evaluated in simulated physiological solution by monitoring the open circuit potential,polarization techniques and electrochemical impedance spectroscopy(EIS).Surface analysis techniques(SEM,EDS,X-ray diffraction and X-ray photoelectron spectroscopy(XPS))were used for coating characterization.The film is mainly composed by cerium and molybdenum oxides and magnesium oxides and hydroxides.The obtained results show that the corrosion resistance of the coated electrodes has been increased significantly.This improvement in the anticorrosive performance is in part due to the corrosion inhibition properties of H_(3)Cit.

Improvement in the corrosion protection and bactericidal properties of AZ91D magnesium alloy coated with a microstructured polypyrrole film

In this work hollow rectangular microtubes of polypyrrole(PPy)films were potentiostatically electrodeposited on magnesium alloy AZ91D in salicylate solution.The substrate was previously anodized under potentiostatic conditions in a molybdate solution in order to improve the adherence of polymer.Finally the duplex film was modified by the incorporation of silver species.The obtained coatings were characterized by scanning electron microscopy(SEM),X-ray diffraction(XRD)and X-ray photoelectron spectroscopies(XPS)and the antimicrobial activity against the bacteria Escherichia coli was evaluated.The corrosion protection properties of the coatings were examined in Ringer solution by monitoring the open circuit potential,polarization techniques and electrochemical spectroscopy(EIS).The duplex coating presents an improved anticorrosive performance with respect to the PPy film.The best results concerning corrosion protection and antibacterial activity were obtained for the silver-modified composite coating.

Friction Stir Processing of Thixoformed AZ91D Magnesium Alloy and Fabrication of Surface Composite Reinforced by SiC_ps

The microstructural evolution characteristics of the thermomechanically affected zone （TMAZ） alloy during friction stir processing （FSP） of thixoformed （TF） AZ91D alloy were investigated. Simultaneously, a surface composite layer reinforced by SiC particles （SiCps） was prepared on the alloy by FSP and the corresponding tribological properties were examined. The experimental results indicate that dynamic recrystallization and mechanical separation （including splitting and fracture of the primary grains） are the main mechanisms of grain refinement for the TMAZ. A composite surface reinforced by uniformly distributed SiCps was prepared on the alloy. Compared with the corresponding permanent mould casting alloy and the TF alloy without composite surface, the TF alloy with composite surface has the highest wear resistance and lowest friction coefficient.

Research on semi-solid thixoforming process of AZ91D magnesium alloy brackets for generators in JH70-type motorbikes

The investment on semi-solid die casting processes of AZ91D magnesium alloy brackets for generators in JH70-type motorbikes is introduced. The processes of low super-heat and cooling slope for the preparation of billets with non-dendritic microstructure, the remelting of billets for thixoforming and the parameters in the process of semi-sohd thixoforming have been researched. The results show that primary billets with non-dendritical structures can be prepared by forming great amount of nuclei in melt via the process of low super heat. By optimizing the remelting process through adjusting the current of the induced equipment, semi-solid billets with a structure of spherical grains were obtained from the primary billets with non-dendritical structure. The range of 580℃ to 583℃ is the proper remelting temperatures by which the billets have an expected thixotropy and can be transferred to a die-casting machine. The optimized parameters of semi-solid forming in a die-casting machine are as follows： the area of the ingate in the die is 383.5 mm^2, the speed of the pierce of the machine 5 m/s, the shot pressure of the pierce 75 MPa, and the maintenance pressure of the pierce 350 MPa. The castings of brackets for supporting generators in JH70 type motorbikes were formed by adopting the optimized processes and parameters mentioned above.

Microstructure of Cu-based Amorphous Composite Coatings on AZ91D Magnesium Alloy by Laser Cladding

To improve the sliding wear resistance of AZ91D magnesium alloy, Cu-based amorphous composite coatings made of CuaTTi34Zr11Nis and Cu47Ti34Zr11Ni8＋20 wt pct SiC powders were fabricated on AZ91D magnesium alloy by laser cladding, respectively. SEM （scanning electron microscopy）, EDS （energy dispersive X-ray spectroscopy）, XRD （X-ray diffraction） and TEM （transmission electron microscopy） techniques were employed to study the phases of the coatings. The results show that the coatings mainly consist of amorphous phase and different intermetallic compounds. The reason of formation of amorphous phase and the function of SiC particles were explained in details.

Effect of Holding Time on Thixotropic Fluidity of Semi-solid AZ91D Magnesium Alloy

To investigate the thixotropic fluidities, microstructures and mechanical properties of semi-solid AZ91D magnesium alloy during reheating, a self-made die set with channels of different sizes were used. The results show that critical forming forces and maximal forming forces could be obtained and related to the holding times in the semi-solid forming process. In the holding time of 0-2700 s, with increasing the holding time, maximal forming force decreased sharply and critical forming force decreased slowly. In the whole thixotropic flowing process, the filling-in was steady and the surface fineness was good. The forming force increased when the slurry changed the flowing direction or flowed from the big-diameter chamber to the small-diameter one. The tensile strength and elongation to failure of the sample after holding time for 2700 s, compared to as-cast sample, are increased by approximately 42.7% and 180%, respectively, and the fractured surfaces presented dimple-like pattern.

Effect of RE on the ignition-proof, microstructure and properties of AZ91D magnesium alloy

The magnesium alloy is prone to burn during die-casting, which limits its applications severely, so the effect of adding rare earth （RE） on the ignition-proof of AZ91D Mg alloy is studied. The results indicate that the addition of mischmetal RE elements has a remarkable influence on the ignition-proof property of the magnesium alloy. It is found that the ignition temperature of the magnesium alloy can be greatly raised by adding a proper amount of RE. When the amount is 0.1wt%, the ignition temperature reaches 877℃ which is 206℃ higher than that of AZ91D without RE and the mechanical properties of the alloy are also improved, However, the amount of RE must be properly controlled because too much RE would induce grain coarsening and reduce the mechanical properties.

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.

Hot deformation behavior and microstructure evolution of as-cast AZ91D magnesium alloy without pre-homogenization treatment

The deformation behavior and the microstruc-ture evolution of as-cast AZ91D magnesium alloy without pre-homogenization treatment were systematically inves-tigated. The flow stress behavior was studied by com-pression tests in strain rate range of 0.001-1.000 s^-1 and deformation temperature range of 220-380 ℃ with a maximum deformation strain of 60 %. The dependence of flow stress on deformation temperature and strain rate was described by hyperbolic sine constitutive equation. Through regression analysis, the average apparent activa- tion energy and coefficient of strain rate sensitivity were estimated to be 181.98 kJ.mol^-1 and 0.14, respectively. The results also reveal that the variation of peak stress depends on strain rate and deformation temperature. Microstructure observation shows that, at temperatures higher than 300 ℃ and strain rates lower than 0.01 s^-1, DRX developed extensively at the grain boundaries and in the core of coarse grains, resulting in a more homogeneous microstructure. Furthermore, the effects of strain, defor-mation temperature, strain rate, and eutectic β phase on the microstructure evolution of as-cast AZ91D magnesium alloy were discussed.

Evaluation of self-healing properties of inhibitor loaded nanoclay-based anticorrosive coatings on magnesium alloy AZ91D

This study emphasizes on the evaluation and comparison of the anticorrosive properties of sol-gel coatings with and without inhibitor loaded nanocontainers.In this case,naturally available clay nanotubes(halloysite)were loaded with cationic corrosion inhibitors Ce 3+/Zr 4+.These nanocontainers were dispersed in hybrid organic-inorganic sol-gel matrix sol.Coating was applied on magnesium alloy AZ91D using the sols containing modified and unmodified nanocontainers employing the dip coating method and cured at 130℃for 1 h in air.Corrosion resistance of coated/uncoated substrates were analyzed using electrochemical impedance spectroscopy,potentiodynamic polarization and weight loss measurements after exposure to 3.5 wt%NaCl solution for varying time durations between 24 h to 120 h.Self-healing ability of coatings was evaluated by micro-Raman spectroscopy after 120 h exposure to 3.5 wt%NaCl solution.Coatings generated after dispersion of corrosion inhibitor loaded clay in hybrid sol-gel matrix have shown more promising corrosion resistance when compared to just the sol-gel matrix coatings,after prolonged exposure to corrosive environment.

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.

Effects of rare earth elements on the microstructure and properties of magnesium alloy AZ91D

The effects of rare earth elements on the microstructure andproperties of magnesium alloy AZ91D alloy were studied. The differentproportion of rare earth elements was added to the AZ91D and thetensile tests were carried out at different temperatures. Theexperimental results show that at room temperature or at 120 deg. Cthe AZ91D's strength decrease with the increasing amount of the rareearth elements. However, the ductility is improved. The influence of0.14/100Sb(mass fraction)on the AZ91D's strength is like that of rareearth elements(0.2/100-0.4/100)(mass fraction). Microstructure graphsdemonstrate that appropriate amount of rare earth elements(0.1/100-0.2/100)can fine AZ91D's grain and improve its ductility.

Effect of phosphate-based sealing treatment on the corrosion performance of a PEO coated AZ91D mg alloy

This study investigated the effect of sealing treatment on the corrosion performance of plasma electrolytic oxidation(PEO)coated AZ91D Mg alloy with and without addition of corrosion inhibitor.The microstructure,phase composition and corrosion property of the sealed and unsealed coatings were evaluated by using scanning electron microscopy(SEM),energy dispersion spectroscopy(EDS),x-ray diffraction(XRD),x-ray photoelectron spectroscopy(XPS),polarization,and electrochemical impedance spectroscopy(EIS)tests.Electrochemical experiments and salt spray tests showed that,after sealing in phosphate solution containing corrosion inhibitor,the corrosion current density of PEO-coated AZ91D decreased more than 10-fold and the anti-corrosion time in a salt spray environment increased more than three-fold.The corrosion rate of the PEO coating slowed down due to the releasing and adsorbing of the corrosion inhibitors in the pores and cracks of the coating during the corrosion process.

Microstructure and tensile properties of thixo-diecast AZ91D magnesium alloy

The thixo-diecasting(TDC)process is the combination of semi-solid billet preparation technology and die casting technology.The TDC process not only keeps the characteristics of thixo-forming but also has high efficiency and low cost.In the present work,the microstructures and mechanical properties of an AZ91D magnesium alloy prepared by the thixo-diecasting(TDC)process were characterized in as-cast condition.The TDC alloy produced exhibits a unique microstructure containingα-Mg solid solution andβ-Mg17Al12intermetallic compound,and there are some small droplets and a small gray globule with eutectic structure in the primaryα-Mg grains.The ultimate tensile strength and elongation of the TDC alloy also increase in comparison with other processes,such as thixocasting.Fracture surface observation shows that a crack mainly originates from the brittle fracture of the eutectic phases.The deformation of ductileα-Mg phase provides the TDC alloy with the main strain.

Release rate kinetics of corrosion inhibitor loaded halloysite nanotube-based anticorrosion coatings on magnesium alloy AZ91D

Halloysite nanotubes were used as nanocontainers to hold corrosion inhibitors such as Ce^(3+)-Zr^(4+),2-mercaptobenzothiazole and 8-hydroxyquinoline in their lumen.An acid assisted etching of the nanotubes was carried out with a view to increase the lumen diameter and thereby,increase the amount of loading of the corrosion inhibitor.The morphology of as-received and etched halloysite nanotubes was ob-served using TEM analysis.The loading of corrosion inhibitors was confirmed using SEM-EDS and BET analysis.Polymeric microcapsules were used as capping agents for the ends of the loaded HNTs following which,they were dispersed into a hybrid sol-gel silica matrix.Dip coating method was used to generate coatings on AZ91D substrates followed by heat treatment at 130℃ for 1 h.The release rate kinetics of corrosion inhibitors from as-received and etched nanotubes was investigated in buffer solutions of 3.5 wt%NaCl at different pH.The release mechanism of corrosion inhibitors from the HNT lumen was validated using various semi-empirical models.Coatings were also evaluated for their corrosion protection ability using electrochemical techniques after exposure to 3.5 wt%NaCl solution for 120 h.Coatings generated using Ce^(3+)-Zr^(4+)loaded into as-received halloysite nanotubes have shown more effective corrosion protection when compared to other corrosion inhibitors after 120 h exposure to the corrosive medium.