Defect Engineering:Can it Mitigate Strong Coulomb Effect of Mg^(2+)in Cathode Materials for Rechargeable Magnesium Batteries?

Rechargeable magnesium batteries(RMBs)have been considered a promising“post lithium-ion battery”system to meet the rapidly increasing demand of the emerging electric vehicle and grid energy storage market.However,the sluggish diffusion kinetics of bivalent Mg^(2+)in the host material,related to the strong Coulomb effect between Mg^(2+)and host anion lattices,hinders their further development toward practical applications.Defect engineering,regarded as an effective strategy to break through the slow migration puzzle,has been validated in various cathode materials for RMBs.In this review,we first thoroughly understand the intrinsic mechanism of Mg^(2+)diffusion in cathode materials,from which the key factors affecting ion diffusion are further presented.Then,the positive effects of purposely introduced defects,including vacancy and doping,and the corresponding strategies for introducing various defects are discussed.The applications of defect engineering in cathode materials for RMBs with advanced electrochemical properties are also summarized.Finally,the existing challenges and future perspectives of defect engineering in cathode materials for the overall high-performance RMBs are described.

Effects of magnesium chloride-based multicomponent salts on atmospheric corrosion of aluminum alloy 2024

Atmospheric corrosion of aluminum alloy 2024 （AA2024） with salt lake water was simulated through a laboratory- accelerated test of cyclic wet-dry and electrochemical techniques. Effects of the soluble magnesium salt contained in the salt water were investigated by scanning electron microscope （SEM）, transmission electron microscope （TEM）, energy dispersive spectrometer （EDS）, electron probe micro analyzer （EPMA）, X-ray diffraction （XRD）, infrared transmission spectroscope （IR）, and atmospheric corrosion monitor （ACM）. The results showed that, with the deposition, atmospheric corrosion of AA2024 could occur when the relative humidity （RH） was lower than 30%. A main crystalline component of corrosion products, layered double hydroxides （LDH）, [Mg1-xAlx（OH）2]^x＋ Clx-·mH2O （LDH-C1）, was determined, which meant that magnesium ion played an important role in the corrosion process. It not only facilitated the corrosion as a result of deliquescence, but also was involved in the corrosion process as a reactant.

Creep mechanism and creep constitutive model of aluminum silicate short-fiber-reinforced magnesium matrix composite

By the constant stress tensile creep test method, creep tests were performed on aluminum silicate short fiber-reinforced AZ91D magnesium matrix composite with volume fraction of 30% and its matrix alloy AZ91D under different temperatures and stresses. The results indicate that the composite and the matrix have the same true stress exponent and true activation energy for creep, which are 3 and 144.63 kJ/mol, respectively. The creep of the composite is controlled by the creep of its matrix, which is mainly the controlling of viscous slip of dislocation, and the controlling of grain boundary slippage as a supplement. The creep constitutive model obtained from the experiment data can well describe the creep deformation pattern of the composite.

EIS Study on Pitting Corrosion of AA5083-H321 Aluminum-Magnesium Alloy in Stagnant 3.5% NaCl Solution

In this research, EIS （electrochemical impedance spectroscopy） technique was utilized to study the pitting corrosion behaviour of AA5083-H321 aluminum-magnesium alloy in 3.5% NaCl solution. Impedance spectra were obtained during 240 h of exposure of the sample to the test solution. The surface and cross-section of the samples were studied by scanning electron microscopy （SEM） and EDAX （energy dispersive analysis of X-ray） analysis. The results indicated that as the resistance of the passive layer on intermetallic particles is very small, this parameter on the sample surface layers is controlled by that of pure passive layer. However, the capacitors in the proposed equivalent circuit are replaced with the constant phase elements （CPE）, due to non-uniformity and occurrence of pitting corrosion on the surface. The outward diffusion of Al^＋3 ions through the passive layer and the thickening of this layer cause the impedance decrease in the first 24 h and increase afterwards. The detachment of intermetallic particles from some of pits and the accumulation of the corrosion products inside some others are factors that prevents the continuation of cathodic reactions on the top of the intermetallic particles.

Role of Chloride Ion and Dissolved Oxygen in Electrochemical Corrosion of AA5083-H321 Aluminum-Magnesium Alloy in NaCl Solutions under Flow Conditions

Flow-induced corrosion consists electrochemical and mechanical components. The present paper has to assessed the role of chloride ion and dissolved oxygen in the electrochemical component of flow induced corrosion for AA5083-H321 aluminum-magnesium alloy which is extensively used in the construction of high-speed boats, submarines, hovercrafts, and desalination systems, in NaCI solutions. Electrochemical tests were carried out at flow velocities of 0, ：2, 5, 7 and 10 m/s, in aerated and deaerated NaCI solutions with different sodium chloride concentrations. The results showed that the high rate of oxygen reduction under hydrodynamic conditions causes an increase in the density of pits on the surface. The increase of chloride ions concentration under flow conditions accelerates the rate of anodic reactions, but have no influence on the cathodic reactions. Thus, in the current work, it was found that under flow conditions, due to the elimination of corrosion products inside the pits, corrosion resistance of the alloy is increased.

Influence of magnesium and aluminum salts on hydrolysis of titanyl sulfate solution

The influence of magnesium and aluminum salts as impurities on the hydrolysis of titanyl sulfate was investigated.The degree of TiOSO4 conversion to hydrated titanium dioxide（HTD） and the particle size of HTD were measured as functions of the concentrations of MgSO4 and Al2（SO4）3 in the TiOSO4 solution.The Boltzmann growth model,which focuses on two main parameters,namely the concentrations of Mg2＋ and Al3＋（ρ（Mg2＋） and ρ（Al3＋）,respectively）,fits the data from the hydrolysis process well with R20.988.The samples were characterized by ICP,SEM,XRD,and laser particle size analyzer.It is found that the addition of Mg SO4 simultaneously improves the hydrolysis ratio and the hydrolysis rate,especially when F（the mass ratio of H2SO4 to TiO2） is high,hydrolysis ratio increases from 42.8% to 83.0%,whereas the addition of Al2（SO4）3 has negligible effect on the chemical kinetics of HTD precipitation during the hydrolysis process,hydrolysis ratio increases from 42.8% to 51.9%.An investigation on the particle size of HTD reveals that the addition of Mg SO4 and Al2（SO4）3 clearly increases the size of the crystallites and decreases the size of the aggregates.

Formation of Aluminum-magnesium Alloy Cup by Hydrodynamic Deep Drawing with Twin-loading Paths

In order to overcome the limitation of hydro-rim deep drawing, a new process of hydrodynamic deep drawing （HDD） with independent radial hydraulic pressure was proposed. By employing the dynamic explicit analytical software ETA/DynaformS.5 which is based on LS-DYNA3D, the effects of independent radia! hydraulic pressure on the stress, strain and the sheet-thickness of aluminum-magnesium cylindrical cup with a hemispherical bottom were analyzed by numerical simulation. The feature of stress distribution is that there exists a stress-dividing circle in the flange, and the radius of dividing circle was determined by theoretical analysis and stimulation. The experimental results indicate that the reasonable match of independent radial hydraulic pressure and liquid chamber pressure can effectively reduce the thinning at the bottom of hemisphere, decrease the radial stress-strain, and improve the drawing limit of aiuminum-magnesium alloy cylindrical cup.

Semi-solid processing of aluminum and magnesium alloys:Status,opportunity,and challenge in China

Owing to its low cost,short process and low energy consumption,semi-solid processing(SSP)of aluminum(Al)and magnesium(Mg)alloys has been considered as a competitive approach to fabricate complicated components with excellent performance.Over the past decade,significant progress has been achieved in deeply understanding the SSP process,the microstructure and performance of the fabricated components in China.This paper starts with a retrospective overview of some common slurry preparation methods,followed by presenting the performance and the underlying mechanisms of SSP fabricated alloys.Then,the mainstream opinions on the microstructure evolution and rheological flow behavior of semi-solid slurry are discussed.Subsequently,the general situation and some recent examples of industrial applications of SSP are presented.Finally,special attention is paid to the unresolved issues and the future directions in SSP of Al and Mg alloys in China.

Influence of silane on corrosion resistance of magnesium alloy AZ31 with thermally sprayed aluminum coatings

Aluminum coatings on Mg alloy AZ31 were fabricated using the thermal spraying technique, and then sealed with silane.The surface morphology and chemical groups were discerned using scanning electron microscopy and examined using Fourier transformation infrared spectroscopy, respectively.The salt fog tests and the potentiodynamic electrochemical technique were applied to evaluate the influence of silane on corrosion of the AZ31 alloy with aluminum coatings.The results showed that the corrosion resistance of the aluminum-coated AZ31 alloy was superior to that of the substrate.The aluminum coating sealed with various silane layers led to a further increase in the corrosion resistance of the alloy.Double silane layers were more corrosion-resistant than the single one.Also, it was no longer significant for more than two silane layers to improve the corrosion resistance.It implied that the optimum choice for silane treatment on the aluminum coatings was two layers.

Determining the microstructure and properties of magnesium aluminum composite panels by hot rolling and annealing

The researchers made magnesium aluminum composite panels by asymmetric metal packaging and studied rolling temperature,holding time,and high temperature heat treatment,such as short time and low temperatures over long periods of time parameters under the new preparation method.We tested the new magnesium aluminum composite panels’tensing properties and bending performance by using scanning electric mirror and EDS.It is concluded that the new magnesium aluminum composite panels’elongation is 24%under the tensile strength of 260 MPa.Regarding performance when compared with other methods,traditional magnesium aluminum composite panels’elongation is 10%,which shows its advanced nature.At the same time,bending performance test showed that the combination of the composite board has higher performance,offering the reference value for the preparation of magnesium–aluminum composite plate.

Improvement on the Corrosion Resistance of AZ91D Magnesium Alloy by Aluminum Diffusion Coating

By combination of magnetron sputtering deposition and vacuum annealing, an aluminum diffusion coating was prepared on the substrate of AZ91D alloy to improve its corrosion resistance. The microstructure and composition of the diffusion coating was investigated by scanning electron microscopy and X-ray diffraction. The diffusion coating was mainly comprised of β phase-Al12Mg17. The continuous immersion test in 3.5 wt pct neutral NaCl solution indicated that the specimen with diffusion coating had better corrosion resistance compared with the bare AZ91D alloy specimen. The potentiodynamic polarization measurement indicated that the diffusion coating could function as an effectively protective layer to reduce the corrosion rate of AZ91D alloy when exposed to 3.5 wt pct NaCl solution.

Predicting and controlling interfacial microstructure of magnesium/aluminum bimetallic structures for improved interfacial bonding

In this study,an overcasting process followed by a low-temperature(200°C)annealing schedule has been developed to bond magnesium to aluminum alloys.ProCAST software was used to optimize the process parameters during the overcasting process which lead to Mg/Al bimetallic structures to be successfully produced without formation of Mg-Al intermetallic phases.Detailed microstructure evolution during annealing,including the formation and growth of Al-Mg interdiffusion layer and intermetallic phases(Al12Mg17 and Al3Mg2),was experimentally observed for the first time with direct evidence,and predicted using Calculation of Phase Diagrams(CALPHAD)modeling.Maximum interfacial strength was achieved when the interdiffusion layer formed at the Mg/Al interface reached a maximum thickness the without formation of brittle intermetallic compounds.The precise diffusion modeling of the Mg/Al interface provides an efficient way to optimize and control the interfacial microstructure of Mg/Al bimetallic structures for improved interfacial bonding.

Aluminum-Magnesium Silicate enhances release of virions of cultured <i>Fowl Pox Virus</i>and inhibits the virus

Antiviral effects of a synthetic Aluminum-Magnesium Silicate (AMS) were tested on Fowl Pox Virus (FPV). Five batches of the Nigerian brand of FPV vaccine were used as sources of the virus. The reconstituted vaccines were mixed with The Synthetic AMS on equal volume to weight basis and incubated at room temperature for one hour. They were centrifuged for 10 minutes at 2000 revolutions per minute. The incubation and centrifugation were repeated on a portion of each vaccine supernatant. The two sets of supernatants were tested by the Modified Passive Haemagglutination test, for FPV titres. Portions of the vaccines, not incubated with the AMS, were served as controls. Fowl Pox Virus titres of the vaccines increased from a mean of 2.8 ± 1.10 to 11.2 ± 4.38 when incubated with the AMS once. When incubation with the AMS was repeated, the titres reduced (P< 0.05) to zero in each sample.

Galvanic Corrosion of Magnesium Alloy and Aluminum Alloy by Kelvin Probe

Galvanic corrosion on samples of AZ91D magnesium alloy coupled with 2A12 aluminum alloy during neutral salt spray test was investigated.The variations of the surface potential were measured using scanning kelvin probe（SKP）.The results showed that galvanic effect on the corrosion of AZ91D magnesium alloy is closely related to the potential difference between the anodic and cathodic materials.In the initial period,corrosion only occurred in a narrow area at the coupling interface because of the limited distance galvanic current.Then,the corrosion rate of 2A12 aluminum alloy was accelerated due to its poor stability in strong alkali environment,which was attributed to the strong alkalization caused by the corrosion of AZ91D magnesium alloy.With the increase of the potential of 2A12 aluminum alloy as a result of the continuous covering of corrosion products,the potential difference between the two materials was enlarged,which enhanced the galvanic corrosion.

Microstructural analyses of aluminum–magnesium–silicon alloys welded by pulsed Nd: YAG laser welding

Revealing grains and very fine dendrites in a solidified weld metal of aluminum–magnesium–silicon alloys is difficult and thus,there is no evidence to validate the micro-and meso-scale physical models for hot cracks. In this research, the effect of preheating on the microstructure and hot crack creation in the pulsed laser welding of AA 6061 was investigated by an optical microscope and field emission electron microscopy. Etching was carried out in the gas phase using fresh Keller’s reagent for 600 s. The results showed that the grain size of the weld metal was proportional to the grain size of the base metal and was independent of the preheating temperature. Hot cracks passed the grain boundaries of the weld and the base metal. Lower solidification rates in the preheated samples led to coarser arm spacing;therefore, a lower cooling rate. Despite the results predicted by the micro and meso-scale models, lower cooling rates resulted in increased hot cracks. The cracks could grow in the weld metal after solidification;therefore, hot cracks were larger than predicted by the hot crack prediction models.

Dissimilar friction stir welding between 5052 aluminum alloy and AZ31 magnesium alloy

Dissimilar friction stir welding between 5052 Al alloy and AZ31 Mg alloy with the plate thickness of 6 mm was investigated.Sound weld was obtained at rotation speed of 600 r/min and welding speed of 40 mm/min.Compared with the base materials,the microstructure of the stir zone is greatly refined.Complex flow pattern characterized by intercalation lamellae is formed in the stir zone.Microhardness measurement of the dissimilar welds presents an uneven distribution due to the complicated microstructure of the weld,and the maximum value of microhardness in the stir zone is twice higher than that of the base materials. The tensile fracture position locates at the advancing side(aluminum side),where the hardness distribution of weld shows a sharp decrease from the stir zone to 5052 base material.

Improving mechanical properties of AZ91D magnesium/A356 aluminum bimetal prepared by compound casting via a high velocity oxygen fuel sprayed Ni coating

In this paper,a Ni coating was deposited on the surface of the A356 aluminum alloy by high velocity oxygen fuel spraying to improve the performance of the AZ91D magnesium/A356 aluminum bimetal prepared by a compound casting.The effects of the Ni coating as well as its thickness on microstructure and mechanical properties of the AZ91D/A356 bimetal were systematically researched for the first time.Results demonstrated that the Ni coating and its thickness had a significant effect on the interfacial phase compositions and mechanical properties of the AZ91D/A356 bimetal.The 10μm’s Ni coating cannot prevent the generation of the Al-Mg intermetallic compounds(IMCs)at the interface zone of the AZ91D/A356 bimetal,while the Ni coating with the thickness of 45μm and 190μm can avoid the formation of the Al-Mg IMCs.When the Ni coating was 45μm,the Ni coating disappeared and transformed into Mg-Mg_(2)Ni eutectic structures+Ni_(2)Mg_(3)Al particles at the interface zone.With a thickness of 190μm’s Ni coating,part of the Ni coating remained and the interface layer was composed of the Mg-Mg_(2)Ni eutectic structures+Ni_(2)Mg_(3)Al particles,Mg_(2)Ni layer,Ni solid solution(SS)layer,Al_(3)Ni_(2) layer,Al_(3)Ni layer and sporadic Al_(3)Ni+Al-Al_(3)Ni eutectic structures from AZ91D side to A356 side in sequence.The interface layer consisting of the Mg-Ni and Al-Ni IMCs obtained with the Ni coating had an obvious lower hardness than the Al-Mg IMCs.The shear strength of the AZ91D/A356 bimetal with a Ni coating of 45μm thickness enhanced 41.4%in comparison with that of the bimetal without Ni coating,and the fracture of the bimetal with 45μm’s Ni coating occurred between the Mg matrix and the interface layer with a mixture of brittle fracture and ductile fracture.

Peculiarities of forming diffusion bimetallic joints of aluminum foam with a monolithic magnesium alloy

The work is carried out to determine an optimal method to obtain the welded bimetallic joints of monolithic Mg-alloy with porous Al-alloy using gallium as chemical activator and heating up to 300 ℃ by two different methods:long-term in vacuum oven and short-term without vacuum by passing of low voltage current.There is no microstructure change in Al-foam but indentation test records the negligible reduction of the mechanical properties.SEM showed the crystallization of two types of Mg_(5)Ga_(2) and Mg_(2)Ga inter-metallic phases in the wavy uneven diffusion zone on Mg-alloy side with significant increase of micro-hardness and Young’s modulus.The narrow depth of the diffusion zone takes place in joints by short-term heating,so this method is more applicable for welding of monolithic and porous alloys at chemical activation using gallium.

Friction self-piercing riveting(F-SPR)of aluminum alloy to magnesium alloy using a flat die

Friction self-piercing riveting(F-SPR)process based on a pip die has been invented to solve the cracking problems in riveting high-strength and low-ductility light metals,such as magnesium alloys,cast aluminum,and 7 series aluminum alloys.In this paper,in order to solve quality issues caused by the misalignment between rivet and pip-die in F-SPR,a flat-die based F-SPR process was proposed and employed to join 1.27 mm-thick AA6061-T6 to 3 mm-thick AZ31B.The results indicate that a 1.0 mm die distance is effective to avoid rivet upset and insufficient flaring.As the feed rate increases,the heat input in the whole process decreases,resulting in a larger riveting force,which in turn increases both the bottom thickness and interlock amount.Besides,solid-state bonding,including Al-Mg intermetallic compounds(IMCs),Al-Mg mechanical mixture,and Al-Fe atom interdiffusion was observed at the joint interfaces.The upper Al layer was softened,but the lower Mg layer was hardened,and both sheets exhibited a narrowed affected region with the increase of feed rate,while the rivet hardness shows no obvious change.Three fracture modes appeared accompanying the variations in lap-shear strength and energy absorption as the feed rate increased from 2 mm/s to 8 mm/s.Finally,the F-SPR process using a flat die was compared to those using a pip die and a flat bottom die to show the advantage of flat die on coping with the misalignment problem.

Influence of Al Content on the Atmospheric Corrosion Behaviour of Magnesium-Aluminum Alloys

The influence of AI content on the Mg-AI alloys corrosion performance during sodium chloride induced atmospheric corrosion has been studied. It was found that the corrosion rate of three Mg-AI alloys was accelerated with increasing AI content. The poor corrosion resistance was attributed to the galvanic coupling between the phase and eutectic phase or α phase and the formation of porous corrosion products.