Formation mechanism of electroless plating nickel-based composite coating on highly active rare earth magnesium alloys and its corrosion resistance and adhesion performance

The process of preparing anodic oxide film containing active sites and electroless nickel plating on highly active rare earth magnesium alloy was developed.The formation mechanism of electroless nickel plating on active anodic oxide film and the structure and properties of the composite coating were studied by several surface and electrochemical techniques.The results showed that Ag nanograins with an average size of 10 nm were embedded into the anodic oxide film with pores of 0.1−2μm.Ag nanoparticles provided a catalytic site for the deposition of Ni-B alloy,and the Ni crystal nucleus was first grown in horizontal mode and then in cylindrical mode.The corrosion potential of the composite coating increased by 1.37 V and the corrosion current reduced two orders of magnitude due to the subsequent deposition of Ni-P alloy.The high corrosion resistance was attributed to the misaligning of these micro defects in the three different layers and the amorphous structure of the Ni-P alloy in the outer layer.These findings provide a new idea for electroless nickel plating on anodic oxide film.

A crystal plasticity based approach to establish role of grain size and crystallographic texture in the Tension–Compression yield asymmetry and strain hardening behavior of a Magnesium–Silver–Rare Earth alloy

Existence of tension–compression yield asymmetry is a serious limitation to the load bearing capablities of Magnesium alloys in a number of light weight structural applications.The present work is aimed at nullifying the tension to compression asymmetry problem and strain hardening anomalies in a Magnesium–Silver–Rare Earth alloy by engineering different levels of microstructural conditions via friction stir processing and post process annealing.The existence and extent of yield asymmetry ratio in the range of microstructural conditions was experimentally obtained through quasistatic tensile and compression tests.The yield asymmetry problem was profoundly present in specimens of coarse grained microstructures when compared to their fine grained and ultra fine grained counterparts.The impact of the microstructure and associated mechanisms of plasticity on the macroscopic strain hardening behavior was established by Kock–Mecking’s analysis.Crystal plasticity simulations using Viscoplastic Self Consistency approach revealed the consequential role of extension twinning mechanism for the existence of yield asymmetry and anomalies in strain hardening behavior.This was especially dominant with coarsening of grain size.Electron Microscopy and characterization were conducted thoroughly in partially deformed specimens to confirm the predictions of the above simulations.The role of crystallographic texture for inducing the polarity to Tension–Compression yield asymmetry was corroborated.A critical grain size in Magnesium–Silver–Rare earth alloy was hereby established which could nullify influences of extension twinning in yield asymmetry ratio.

The effect of LPSO on the deformation mechanism of Mg-Gd-Y-Zn-Zr magnesium alloy

The tensile deformation behavior and corresponding microstructure evolution of the Mg-4.7Gd-3.4Y-1.2Zn-0.5Zr(at.%)magnesium alloy with long period stacking structure(LPSO)are studied by electron backscatter diffraction(EBSD)and slip lines methods.The results show that less and very small size of twins is observed in the grains with high value of Schmid factor for twinning,which indicates that the growth of the{10–12}twinning deformation is prevented by the LPSO phase.The prismatic lines present in grains of which the prismatic slip Schmid factor is above 0.4.The favorable orientation and LPSO phase synergistically promote the activation of prismatic slip.The inhomogeneous rotation of the grains during deformation is the reason for the microcrack at grain boundary.

Thermodynamics and kinetics of phase transformation in rare earth–magnesium alloys:A critical review

Magnesium and its alloys are significant superior metallic materials for structural components in automobile and aerospace industries due to their excellent physicomechanical properties.The Mg–rare earth(RE)systems have attracted great interests because RE additions can improve both the deformability and the strength of Mg alloys through solid solution strengthening and precipitation hardening mechanisms.This paper focuses on the interface stability,together with thermodynamics and kinetics of nucleation and growth of the key phases and matrix phases in Mg–RE alloys.In this paper,the theory and recent advances on Mg–RE alloys,especially for the interface stability,thermodynamics and kinetics of nucleation and growth of the key phases and matrix phases,together with their relationships with micro-structures,and macroscopic properties,are reviewed.By combining the thermodynamics/kinetics integrated simulations with various advanced experimental techniques,“reverse”design of Mg–RE alloys starting from the target service performance is put forward as a kind of scientific paradigm with rational design.

Environmentally assisted cracking behavior of U-bend specimens of Mg-RE alloys in chloride containing basic solution

Environmentally assisted cracking(EAC)behavior of two Mg-rare earth(RE)alloys such as Mg-Zn-Gd-Nd-Zr(EV31A)and Mg-Y-Nd(WE43C)alloys was investigated by using U-bend specimens.Open circuit potentials(OCP)of the U-bend specimens were monitored during the EAC tests in 0.1 M NaOH solution with different chloride concentrations at room temperature.EV31A(as-received,and peak aged)and WE43C(peak aged)specimens failed by SCC in 80 ppm chloride containing 0.1 M NaOH solution at OCP.When the EAC initiation occurred,the OCP decreased continuously.Irregular fluctuations of the OCP were observed in the absence of EAC.The OCP versus time profile could be used for monitoring EAC failure of the Mg-RE alloy components in real life service.Applied potentials did not cause cracking of the EV31A alloy in 80 ppm Cl-containing 0.1 M NaOH.Accelerated cracking was observed on the WE43C alloy in peak-aged condition under the applied potentials in the transpassive region when compared to that of OCP condition.Overaging decreased the susceptibility to cracking.

Multi-scale simulation of columnar-to-equiaxed transition during laser selective melting of rare earth magnesium alloy

A model of coupling macro finite volume method(FVM) and cellular automata(CA) is proposed in this paper to explore the columnar-to-equiaxed transition(CET) during selective laser melting(SLM) of rare earth magnesium alloy.Taking into account the impact of recoil pressure and Marangoni convection on the molten pool temperature field,the grain structure is simulated.As suggested by the simulation results,with the undissolved Zr serving as heterogeneous nucleation sites,the liquid undercooled layer under the combined action of forced cooling,the temperature gradient and the liquid solute concentration gradient leads to CET.While considering the dissolution of Zr in magnesium matrix,the results demonstrate that the dissolution of element Zr is effective in significantly inhibiting the growth of columnar crystals and ensuring the sufficient constitutional supercooling(CS) required for nucleation.In addition,to raise the preheating temperature contributes to enhancing the outcome of nucleation and incresing the grain size.Invoking the interdependence model(IM),with the cooling rate gradually increasing in the SLM process of magnesium alloy,the nucleation-free zone(NFZ) reduces by decreasing the solute diffusion layer in the front of the solid/liquid(SL) interface and the temperature gradient.The reduction in temperature gradient can promote undercooling for nucleation and facilitate the development of equiaxed crystals.The simulation results are qualitatively verified as highly consistent through experimentation.

Passivation kinetics of Mg-Nd-Gd-Zn-Zr(EV31A)and Mg-Y-Nd-Gd-Zr(WE43C)in NaOH solutions

Passivation kinetics of two Mg-RE alloys,such as Mg-Nd-Gd-Zn-Zr(EV31A),and Mg-Y-Nd-Gd-Zr(WE43C)were investigated in two different heat treated conditions(solution treated and overaged)in 0.01-1.0 M NaOH solutions under potentiostatic conditions.Negative reaction order was observed in dilute NaOH which transitioned to positive values as the passivation time increased and in the 1 M NaOH as well.The passive layers showed platelet morphology and the size of the platelets decreased with increase in the NaOH concentration.The hydrogen evolution reaction(HER)kinetics was not improved on the passive layer covered surface of the Mg-RE alloys in contrast to the improvements reported on the hydroxide covered pure magnesium.The electrochemical impedance increased with increase in the NaOH concentration in the solution treated condition of both Mg-RE alloys,whereas the overaged EV31A alloy showed a reverse trend.The passive layer of EV31A showed almost 100%higher charge carrier density than the film formed on the WE43C in the overaged condition.A better passivation behavior was observed in the solution treated condition than that in the overaged condition which could be attributed to the uniform distribution of the RE elements in the solution treated specimens.The WE43C alloy revealed better corrosion resistance in the alkaline solution than the EV31A alloy.

Effect of Ca and Y additions on oxidation behavior of magnesium alloys at high temperatures

Oxidation and ignition of magnesium alloys at elevated temperature were successfully retarded by additions of Y and Ca,which could be melted at 1173 K in air without any protection.Thermogravimetric measurements in dry air revealed that the oxidation dynamics curves of Mg-2.5Ca alloy and Mg-3.5Y-0.79Ca alloy at high temperatures followed the parabolic-line law or the cubic-line law.X-ray diffraction（XRD） and scanning electron microscopy（SEM） analysis indicated that the oxide film on the surface of Mg-3.5Y-0.79Ca and Mg-2.5Ca alloys exhibited a duplex structure,which agreed with the results of thermodynamic analysis.By comparison,the ignition-proof effect of the combination addition of Y and Ca was better than that of the single addition of Ca.

Effect of solidification mode on microstructure evolution and properties of magnesium alloy with long-period stacking ordered phase

The solidification methods of electromagnetic stirring(EMS)and non-electromagnetic stirring were employed to prepare Mg–6Gd–3Y–xZn–0.6Zr(x=1,1.5,2,3)alloys.The evolution of alloy microstructures and the changes in properties were analyzed for different Zn contents.It has been observed that in alloys without electromagnetic stirring,as the Zn content increases,the alloy structure gradually refines.The primary second phase transitions from Mg5RE phase to long-period stacking ordered(LPSO)phase,resulting in improved hardness and elongation.In alloys subjected to electromagnetic stirring,there is a relatively higher content of the second phase,primarily consisting of LPSO phase.After applying electromagnetic stirring,the quantity and the type of LPSO phase in the alloy change.The alloy structure becomes more uniform with electromagnetic stirring,resulting in increased hardness and reduced hardness gradients within the grains.The mechanical properties of alloys with electromagnetic stirring are superior to those without electromagnetic stirring.

Effect of homogenization on microstructure and properties of WE91 alloys

The microstructure and properties of the Mg-9Y-1MM-0.6Zr alloy were studied by scanning electron microscopy, optical microscopy, transmission electron microscopy, hardness and tensile testing. Homogenization was confirmed, and the solidification model was established. The as-cast alloy was mainly composed of ct-Mg and eutectic structures. The suitable homogenization pa- rameters were 535℃ for 18 h. Most of the eutectic structure dissolved in this process. Only the Mg4.26Y95.74 and Mg12 （MM） phases were remained in, and only a few microstructure occurred for prolonged time. The ultimate tensile strength of the alloy increased up to 232 MPa after homogenization, but the yield strength and the elongation were almost as same as the as-cast state. In the as-cast al- loys the cracks started in the eutectic structure, and then intergranular fracture occurred, but in the homogenate alloys residual phases became the source of the cracks and then tmnscrystalline fracture took place. The most important roles of homogenization were the decomposition of the eutectic structure, furthermore the intergranular fracture turned into a transcrystalline fracture, which was one of the main reasons to increase the strength of the alloys.

Microstructure and texture evolution of Mg–7Y–1Nd–0.5Zr alloy sheets with different rolling temperatures

The extruded Mg-7Y-1Nd-0.5Zr(wt%)alloy were performed to the same strain hot rolling with different temperatures.The microstructure and texture evolution of the sheets were investigated by optical microscopy(OM),scanning electron microscopy(SEM),transmission electron microscopy(TEM),X-ray diffraction(XRD),and electron back-scattered diffraction(EBSD).The results indicate that the microstructure becomes homogeneous after hot rolling process and precipitated phase distributes at grain boundaries along rolling direction.With the increase in rolling temperature,the grains of sheet grow up.The sheet rolling at 400℃is composed of recrystallization grains,the necklace of the precipitated phase in the grain boundaries and excessive dislocations.The structure of necklace of the precipitated phase is fcc structure with lattice constant of a=0.75 nm.With rolling temperatures increasing from 400 to 450℃,the content of recrystallized grains in volume fraction with relatively random orientations increases significantly.Compared with the rolling process at 400℃,the amount of precipitated phases is reduced at the grain boundary,and the precipitated phase begins to appear in the grain interior when rolling at 450℃.The structure of the precipitated phase is fcc with lattice constant of a=2.22 nm.The recrystallization grains begin to grow in the rolling process at 500℃.The basal texture is obviously produced during the rolling process at 400 and 450℃;however,the basal texture is weak in the rolling process at 500℃.

Homogenization heat treatment of Mg-7.0 wt%Y-1.0 wt%Nd-0.5 wt%Zr alloy

The microstructures and mechanical properties of Mg-7.0 wt%Y-1.0 wt%Nd-0.5 wt%Zr magnesium alloy were investigated both in as-cast condition and after homogenization heat treatment by differential scanning calorimetry(DSC),optical microscopy(OM),X-ray diffraction(XRD),scanning electron microscopy(SEM)and hardness measurement.The results indicate that the ascast alloy consists ofα-Mg matrix,Mg24 Y5 and Mg41 Nd5 phases,which are eutectic phases(cubic Y-rich phase).With the increase in homogenization temperature and time,the Mg24 Y5 and Mg41 Nd5 phases are completely dissolved into matrix,and only yttrium of intermetallic compounds leaves around boundary.After homogenization heat treatment,the elements distributed uniformly and the grains grow up not obviously,only yttrium element of intermetallic compounds left around boundary.The optimum homogenization condition is at 537℃for 16 h.The mechanical properties are improved after homogenization,with tensile strength ofσb=181 MPa,yielding strength ofσ(0.2)=144 MPa and elongation ofδ=5.5%,which are better than those of as-cast alloy.

Superior Properties of Mg–4Y–3RE–Zr Alloy Prepared by Powder Metallurgy

Magnesium alloys are important materials for application in the automotive and aviation industries. During the last few years, the number of possible applications as biodegradable implants in medicine has grown. Mg-RE（rare earth） alloys belong to the most advanced group of products, offering the best combination of mechanical properties and corrosion resistance. Among these materials, WE43（Mg-Y-Nd）is a very well-known commercial alloy that has been extensively studied for applications at increased temperatures and also in organisms. Although this material has been described, there are still possibilities to improve its properties and subsequently expand its applicability. Powder metallurgy has already been used for the preparation of magnesium alloys with superior mechanical properties and occasionally superior corrosion properties. Therefore, the present paper is oriented toward the preparation of Mg-4Y-3RE-Zr（WE43） alloy by the powder metallurgy technique（WE43-PM） and comparison of the final properties with the product of extrusion of as-cast ingot（WE43-IM）. Our processing leads to a partial improvement in the mechanical properties and superior corrosion resistance of WE43-PM. The texture strength of WE43-PM was low, and therefore, anisotropy of mechanical properties was suppressed.