Greatly enhanced corrosion/wear resistances of epoxy coating for Mg alloy through a synergistic effect between functionalized graphene and insulated blocking layer

The poor corrosion and wear resistances of Mg alloys seriously limit their potential applications in various industries.The conventional epoxy coating easily forms many intrinsic defects during the solidification process,which cannot provide sufficient protection.In the current study,we design a double-layer epoxy composite coating on Mg alloy with enhanced anti-corrosion/wear properties,via the spin-assisted assembly technique.The outer layer is functionalized graphene(FG)in waterborne epoxy resin(WEP)and the inner layer is Ce-based conversion(Ce)film.The FG sheets can be homogeneously dispersed within the epoxy matrix to fill the intrinsic defects and improve the barrier capability.The Ce film connects the outer layer with the substrate,showing the transition effect.The corrosion rate of Ce/WEP/FG composite coating is 2131 times lower than that of bare Mg alloy,and the wear rate is decreased by~90%.The improved corrosion resistance is attributed to the labyrinth effect(hindering the penetration of corrosive medium)and the obstruction of galvanic coupling behavior.The synergistic effect derived from the FG sheet and blocking layer exhibits great potential in realizing the improvement of multi-functional integration,which will open up a new avenue for the development of novel composite protection coatings of Mg alloys.

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.

Effect of pre-twinning and heat treatment on formability of AZX311 Mg alloy

In this study,the effects of pre-strain-induced tensile twins(TTWs)and controlled heat treatment on the formability behavior of AZX311 Mg alloy sheets were investigated.A 4%compressive strain was applied to pre-strain the sheets using the in-plane compression(IPC)technique along the rolling direction(RD)to introduce TTWs.The pre-strained(PS)samples were subsequently heat-treated at 250℃,350℃,and 400℃ independently for 1 hr,and are termed as PSA1,PSA2,and PSA3,respectively.Erichsen cupping tests were conducted to assess the formability of the sheet samples under different initial conditions.The results showed that the PS sample heat-treated at 250℃ for 1hr exhibited a decrease in the Erichsen index(IE)compared to the as-rolled sample,whereas PSA2 and PSA3 samples showed an increase in IE values.Microtexture analysis revealed that most of the TTWs generated through pre-twinning were stable at 250℃;however,the twin volume fraction reduced to 41%at 350℃ compared to the PS samples due to enhanced thermal activity at that temperature.Furthermore,PSA2 samples showed severe grain coarsening in some areas of the sample,and the fraction of such grains increased in the PSA3 samples.The stretch formability(IE value)of PSA2 samples showed a 32.3%increase compared to the as-rolled specimens.Additionally,the analysis of the deformed specimen at failure under the Erichsen test indicated that considerable detwinning occurs in the PS and PSA1 samples,whereas dislocation slip activity dominates in the PSA2 and PSA3 samples during stretch forming.Apart from detwinning and dislocation slip,deformation twins were also observed in all samples after the Erichsen test.Thus,this work highlights the importance of texture control and its underlying mechanisms via pre-twinning followed by heat treatment and their impact on the room temperature(RT)stretch formability of AZX311 Mg alloy sheets.

Revealing the role of pyramidal slip in the high ductility of Mg-Li alloy

The high ductility of Mg-Li alloy has been mainly ascribed to a high activity of pyramidal<c+a>slip to accommodate plastic strain.In the present study,however,a quantitative analysis reveals that Li-addition can only slightly stimulate the activation of pyramidal<c+a>slip under compression along the normal direction of a hot-rolled Mg-4.5 wt.%Li plate,with a relative activity of approximately 18%.Although the limited activity of pyramidal<c+a>slip alone cannot accommodate a large plastic strain,it effectively reduces the number of{10.11}−{10.12}double twins,which are believed to be favorable sites for crack initiation.The evidently reduced activity of double twins leads to a lower cracking tendency,and therefore improves ductility.

Twinning aspects and their efficient roles in wrought Mg alloys:A comprehensive review

Twinning is widely recognized as an effective and cost-efficient method for controlling the microstructure and properties of wrought magnesium(Mg)alloys.Specifically,twins play a crucial role in initiating dynamic recrystallization(DRX),while twin regions experience rapid recrystallization during static recrystallization(SRX).The activation of twinning can lead to changes in lattice orientation,significantly impacting the final texture in Mg alloys.The active roles of twinning are influenced by various factors during the activation process,and the mobility of twin boundaries(TB)can be amplified by stress effects,dislocation interactions,and thermal effects.Conversely,annealing treatments that involve proper segregation or precipitation on TBs serve to stabilize them,restraining their motion.Events such as segregation may also alter the twinning propensity in Magnesium-rare earth(Mg-RE)alloys.While{10–11}contraction twins(CT)and{10–11}-{10–12}double twins(DT)can promote dynamic recrystallization(DRX),they also pose a risk as potential sources of voids and cracks.Additionally,understanding the nucleation and growth mechanisms of twinning is crucial,and these aspects are briefly reviewed in this article.Considering the factors mentioned above,this article summarizes the recent research progress in this field,shedding light on advancements in recent eras.

Effect of characteristics and distribution of Mg_(17)Al_(12)precipitates on tensile and bending properties of high-Al-containing Mg alloys

This study investigates the effect of characteristics and distribution of Mg_(17)Al_(12)precipitates on the uniaxial tensile and three-point bending properties of extruded Mg alloys containing high Al contents.The extruded Mg–9Al–1Zn–0.3Mn(AZ91)alloy contains lamellar-structured Mg_(17)Al_(12)discontinuous precipitates along the grain boundaries,which are formed via static precipitation during natural air cooling.The extruded Mg–11Al–1Zn–0.3Mn(AZ111)alloy contains spherical Mg_(17)Al_(12)precipitates at the grain boundaries and inside the grains,which are formed via dynamic precipitation during extrusion.Due to inhomogeneous distribution of precipitates,the AZ111 alloy consists of two different precipitate regions:precipitate-rich region with numerous precipitates and finer grains and precipitate-scarce region with a few precipitates and coarser grains.The AZ111 alloy exhibits a higher tensile strength than the AZ91 alloy because its smaller grain size and more abundant precipitates result in stronger grain-boundary hardening and precipitation hardening effects,respectively.However,the tensile elongation of the AZ111 alloy is lower than that of the AZ91 alloy because the weak cohesion between the dynamic precipitates and the matrix facilitates the crack initiation and propagation.During bending,a macrocrack initiates on the outer surface of bending specimen in both alloys.The AZ111 alloy exhibits higher bending yield strength and lower failure bending strain than the AZ91 alloy.The bending specimens of the AZ91 alloy have similar bending formability,whereas those of the AZ111 alloy exhibit considerable differences in bending formability and crack propagation behavior,depending on the distribution and number density of precipitates in the specimen.In bending specimens of the AZ111 alloy,it is found that the failure bending strain(ε_(f,bending))is inversely proportional to the area fraction of precipitates in the outer zone of bending specimen(A_(ppt)),with a relationship ofε_(f,bending)=–0.1A_(ppt)+5.86.

Structural,mechanical and electronic properties of precipitates in Mg−Zn alloys

To accelerate the development and design of magnesium(Mg)alloys,the structural and mechanical properties of important precipitates in Mg−Zn alloys were studied by experiments and density functional theory.The nano-indentation tests revealed that the hardness of the precipitates initially increased and then decreased with increasing Zn content,and was significantly higher than that of pure Mg and Zn.The calculation results revealed that the precipitates stability initially increased and then decreased with increasing Zn concentration.The bulk moduli of the precipitates increased,whereas their shear and Young’s moduli initially increased and then decreased with increasing Zn content.The decreasing order of ductility for these compounds is MgZn_(2)>Mg21Zn_(2)5>Mg2Zn11>Mg4Zn7.The surface profiles of the compounds revealed that they are obvious anisotropy.Both the degree of covalency and bond length of covalent bonds initially increased and then decreased with increasing Zn content.

In situ TEM investigation of electron irradiation and aging-induced high-density nanoprecipitates in an Mg-10Gd-3Y-1Zn-0.5Zr alloy

In-situ electron irradiation and aging are applied to introduce high-density precipitates in an Mg-10Gd-3Y-1Zn-0.5Zr(GWZ1031K,wt.%)alloy to improve the hardness.The results show that the hardness of the Mg alloy after irradiation for 10 h and aging for 9 h at 250℃ is 1.64 GPa,which is approximately 64% higher than that of the samples before being treated.It is mainly attributed to γ'precipitates on the basal plane after irradiation and the high-density nanoscale β'precipitates on the prismatic plane after aging,which should be closely related to the irradiation-induced homogenous clusters.The latter plays a key role in precipitation hardening.This result paves a way to improve the mechanical properties of metallic materials by tailoring the precipitation through irradiation and aging.

Development of anti-corrosive coating on AZ31 Mg alloy modified by MOF/LDH/PEO hybrids

The self-assembly of hybrid inorganic-organic materials on stationary platforms plays a critical role in improving their structural stability and wide usability.In this work,a novel two-step hydrothermal approach is proposed for synthesizing stable and advanced hybrid coatings on metal-oxide platforms through the surface modification of layered double hydroxide(LDH)films using novel metal-organic frameworks(MOFs).Initially,Mg-Al LDH nanocontainers,grown on a magnesium oxide layer produced through plasma electrolytic oxidation(PEO)of AZ31 Mg alloy substrate,were intercalated with cobalt via an oxidation route,providing the metallic coordination center for the MOF formation.In the subsequent step,a pioneering technique is introduced,utilizing tryptophan as the organic linker for the first time at a pH of 10.The self-assembly of cobalt-tryptophan complex,driven by the strong bonding between electrophilic sites of monomers and nucleophilic sites,facilitated the formation of a MOF network having a cloud-like structure on the surface of MgAl LDH's film.The resulting MOF-LDH encapsulation containers demonstrate exceptional electrochemical stability when exposed to a 3.5 wt.%NaCl solution,surpassing the performance of PEO and pure LDH coatings.This enhanced stability is attributed to the development of a dense top layer and a stable composition within the self-assembled MOF,effectively sealing flaws and preventing the infiltration of corrosive ions into the underlying metallic substrate.The formation mechanism of MOFs on LDH galleries is investigated using density functional theory calculations.

Antibacterial HA-coatings on bioresorbable Mg alloy

In this study,a calcium-phosphate coating was formed on a Mg-Mn-Ce alloy by the plasma electrolytic oxidation(PEO).The antibiotic vancomycin,widely used in the treatment of infections caused by Staphylococcus aureus(S.aureus),was impregnated into the coating.Samples with vancomycin showed high bactericidal activity against S.aureus.The mechanical and electrochemical properties of the formed coatings were studied,as well as in vitro cytotoxicity tests and in vivo tests on mature male rats were performed.According to SEM,EDS,XRD and XPS data,coatings had a developed morphology and contained hydroxyapatite,which indicates high biocompatibility.The analysis of roughness of coatings without and with vancomycin did not reveal any differences,confirming the high roughness of the samples.During electrochemical tests,an increase in corrosion resistance by more than two times after the application of PEO coatings was revealed.According to the results of an in vivo study,after 28 days of the implantation of samples with calcium phosphate PEO coating and vancomycin,no signs of inflammation were observed,while an inflammatory reaction developed in the area of implantation of bare alloy,followed by encapsulation.Antibiotic release tests from the coatings show a sharp decrease in the concentration of the released antibiotic on day 7 and then a gradual decrease until day 28.Throughout the experiment,no significant deviations in the condition and behavior of the animals were observed;clinical tests did not reveal a systemic toxic reaction.

Precipitation of multi-type nano-quasicrystals in a Mg-Zn-Y alloy

Mg-6Zn-1Y(at.%)ribbons with strengthening precipitates of multi-type nanoquasicrystals were prepared by melt-spinning followed by aging treatments.Microstructural evolution of the rapidly solidified ribbons during isothermal aging was comprehensively studied using various electron microscopy techniques.Two new kinds of decagonal quasicrystals were formed in aged ribbons,in addition to precipitation of nanometer icosahedral quasicrystals.Atomic-resolution observations reveal that both decagonal quasicrystals can be modeled by quasiperiodic tiling with decagonal clusters of 2.5 nm in diameter,but overlap of neighboring clusters in both decagonal quasicrystals is different from the Gummelt model observed in other quasicrystals.A shell composed of complex Laves Mg-Zn domains was formed surrounding each decagonal quasicrystal precipitate upon prolonged aging.In addition,all kinds of nanoprecipitates exhibit excellent structure and size stability at 573 K.Our findings may have implications for not only fundamental studies about quasicrystals,but also microstructural manipulation of high-performance Mg alloys.

{1012}twin–twin intersection-induced lattice rotation and dynamic recrystallization in Mg–6Al–3Sn–2Zn alloy

This study investigated the formation mechanism of new grains due to twin–twin intersections in a coarse-grained Mg–6Al–3Sn–2Zn alloy during different strain rates of an isothermal compression.The results of electron backscattered diffraction investigations showed that the activated twins were primarily{1012}tension twins,and 60°<1010>boundaries formed due to twin–twin intersections under different strain rates.Isolated twin variants with 60°<1010>boundaries transformed into new grains through lattice rotations at a low strain rate(0.01 s^(−1)).At a high strain rate(10 s^(−1)),the regions surrounded by subgrain boundaries through high-density dislocation arrangement and the 60°<1010>boundaries transformed into new grains via dynamic recrystallization.

The deteriorated degradation resistance of Mg alloy microtubes for vascular stent under the coupling effect of radial compressive stress and dynamic medium

The degradation of Mg alloys relates to the service performance of Mg alloy biodegradable implants.In order to investigate the degradation behavior of Mg alloys as vascular stent materials in the near service environment,the hot-extruded fine-grained Mg-Zn-Y-Nd alloy microtubes,which are employed to manufacture vascular stents,were tested under radial compressive stress in the dynamic Hanks'Balanced Salt Solution(HBSS).The results revealed that the high flow rate accelerates the degradation of Mg alloy microtubes and its degradation is sensitive to radial compressive stress.These results contribute to understanding the service performance of Mg alloys as vascular stent materials.

Effects of processing parameters on fabrication defects,microstructure and mechanical properties of additive manufactured Mg–Nd–Zn–Zr alloy by selective laser melting process

Mg–3Nd–0.2Zn–0.4Zr(NZ30K,wt.%)alloy is a new kind of high-performance metallic biomaterial.The combination of the NZ30K Magnesium(Mg)alloy and selective laser melting(SLM)process seems to be an ideal solution to produce porous Mg degradable implants.However,the microstructure evolution and mechanical properties of the SLMed NZ30K Mg alloy were not yet studied systematically.Therefore,the fabrication defects,microstructure,and mechanical properties of the SLMed NZ30K alloy under different processing parameters were investigated.The results show that there are two types of fabrication defects in the SLMed NZ30K alloy,gas pores and unfused defects.With the increase of the laser energy density,the porosity sharply decreases to the minimum first and then slightly increases.The minimum porosity is 0.49±0.18%.While the microstructure varies from the large grains with lamellar structure inside under low laser energy density,to the large grains with lamellar structure inside&the equiaxed grains&the columnar grains under middle laser energy density,and further to the fine equiaxed grains&the columnar grains under high laser energy density.The lamellar structure in the large grain is a newly observed microstructure for the NZ30K Mg alloy.Higher laser energy density leads to finer grains,which enhance all the yield strength(YS),ultimate tensile strength(UTS)and elongation,and the best comprehensive mechanical properties obtained are YS of 266±2.1 MPa,UTS of 296±5.2 MPa,with an elongation of 4.9±0.68%.The SLMed NZ30K Mg alloy with a bimodal-grained structure consisting of fine equiaxed grains and coarser columnar grains has better elongation and a yield drop phenomenon.

Effect of nano-CaO particle on the microstructure,mechanical properties and corrosion behavior of lean Mg-1Zn alloy

The effects of nano-CaO contents on the microstructure,mechanical properties and corrosion resistance of lean Mg-1Zn alloy were investigated.The results showed that the addition of nano-CaO significantly refined the grain size and improved mechanical properties of the Mg-1Zn alloy.At the same time,CaO reacted with molten Mg in situ to form nano-MgO,whose corrosion product in SBF solution was the same with the degradation product of Mg matrix,resulting in the enhanced compactness of the Mg(OH)_(2) layer and reduced corrosion rate of matrix.The Mg-1Zn alloy had lower corrosion resistance due to excessively large grain size and shedding of corrosion products.The composite with 0.5 wt.%CaO had the best corrosion resistance with a weight loss of 9.875 mg·y^(-1)·mm^(-2)due to the small number of Ca_(2)Mg_(6)Zn_(3) phase and suitable grain size.While for composites with high content of CaO(0.7 wt.%and 1.0 wt.%),they had lower corrosion resistance due to the coexistence of large number of Ca_(2)Mg_(6)Zn_(3) and Mg_(2)Ca at grain boundaries,especially for 1.0 wt.%CaO composite,resulting from the strong micro-galvanic corrosion.

Study on the low mechanical anisotropy of extruded Mg-Zn-Mn-Ce-Ca alloy tube in the compression process

In this study,the extruded Mg-Zn-Mn-Ce-Ca alloy tube with a low compression anisotropy along the ED,45ED and TD was prepared.The effect of the second phases,initial texture and deformation behavior on this low mechanical anisotropy was investigated.The results revealed that the alloy tube contains the high content(Mg1-xZnx)11Ce phase and the low content of Mg12Ce phase.These second phases are respectively incoherent and coherent with the Mg matrix,and their influence can be ignored.Additionally,the alloy tube exhibited a weak basal fiber texture,where the c-axis was aligned along the 0°∼30°tilt from TD to ED.Such a texture made the initial deformation(at 1.0%∼1.6%strain)of the three samples controlled by comparable basalslip.As deformation progressed(1.6∼9.0%strain),larger amounts of ETWs nucleated and gradually approached saturation in the three samples,re-orienting the c-axis to a 0°∼±30°deviation with respect to the loading directions.Meanwhile,the prismatic and pyramidal<c+a>slips replaced the dominant deformation progressively until fracture.Eventually,the similar deformation mechanisms determined by the weak initial texture in the three samples contribute to the comparable strain hardening rates,resulting in the low compressive anisotropy of the alloy tube.

Two-stage dynamic recrystallization and texture evolution in Al-7Mg alloy during hot torsion

Hot torsion tests were performed on the Al-7Mg alloy at the temperature ranging from 300 to 500℃ and strain rates between 0.05 and 5 s^(-1) to explore the progressive dynamic recrystallization(DRX)and texture behaviors.The DRX behavior of the alloy manifested two distinct stages:Stage 1 at strain of≤2 and Stage 2 at strains of≥2.In Stage 1,there was a slight increase in the DRXed grain fraction(X_(DRX))with predominance of discontinuous DRX(DDRX),followed by a modest change in X_(DRX) until the transition to Stage 2.Stage 2 was marked by an accelerated rate of DRX,culminating in a substantial final X_(DRX) of~0.9.Electron backscattered diffraction(EBSD)analysis on a sample in Stage 2 revealed that continuous DRX(CDRX)predominantly occurred within the(121)[001]grains,whereas the(111)[110]grains underwent a geometric DRX(GDRX)evolution without a noticeable sub-grain structure.Furthermore,a modified Avrami’s DRX kinetics model was utilized to predict the microstructural refinement in the Al-7Mg alloy during the DRX evolution.Although this kinetics model did not accurately capture the DDRX behavior in Stage 1,it effectively simulated the DRX rate in Stage 2.The texture index was employed to assess the evolution of the texture isotropy during hot-torsion test,demonstrating significant improvement(>75%)in texture randomness before the commencement of Stage 2.This initial texture evolution is attributed to the rotation of parent grains and the substructure evolution,rather than to an increase in X_(DRX).

Stress-corrosion coupled damage localization induced by secondary phases in bio-degradable Mg alloys:phase-field modeling

In this study,a phase-field scheme that rigorously obeys conservation laws and irreversible thermodynamics is developed for modeling stress-corrosion coupled damage(SCCD).The coupling constitutive relationships of the deformation,phase-field damage,mass transfer,and electrostatic field are derived from the entropy inequality.The SCCD localization induced by secondary phases in Mg is numerically simulated using the implicit iterative algorithm of the self-defined finite elements.The quantitative evaluation of the SCCD of a C-ring is in good agreement with the experimental results.To capture the damage localization,a micro-galvanic corrosion domain is defined,and the buffering effect on charge migration is explored.Three cases are investigated to reveal the effect of localization on corrosion acceleration and provide guidance for the design for resistance to SCCD at the crystal scale.

Advancements in enhancing corrosion protection of Mg alloys:A comprehensive review on the synergistic effects of combining inhibitors with PEO coating

Magnesium(Mg)alloys are lightweight materials with excellent mechanical properties,making them attractive for various applications,including aerospace,automotive,and biomedical industries.However,the practical application of Mg alloys is limited due to their high susceptibility to corrosion.Plasma electrolytic oxidation(PEO),or micro-arc oxidation(MAO),is a coating method that boosts Mg alloys'corrosion resistance.However,despite the benefits of PEO coatings,they can still exhibit certain limitations,such as failing to maintain long-term protection as a result of their inherent porosity.To address these challenges,researchers have suggested the use of inhibitors in combination with PEO coatings on Mg alloys.Inhibitors are chemical compounds that can be incorporated into the coating or applied as a post-treatment to further boost the corrosion resistance of the PEO-coated Mg alloys.Corrosion inhibitors,whether organic or inorganic,can act by forming a protective barrier,hindering the corrosion process,or modifying the surface properties to reduce susceptibility to corrosion.Containers can be made of various materials,including polyelectrolyte shells,layered double hydroxides,polymer shells,and mesoporous inorganic materials.Encapsulating corrosion inhibitors in containers fully compatible with the coating matrix and substrate is a promising approach for their incorporation.Laboratory studies of the combination of inhibitors with PEO coatings on Mg alloys have shown promising results,demonstrating significant corrosion mitigation,extending the service life of Mg alloy components in aggressive environments,and providing self-healing properties.In general,this review presents available information on the incorporation of inhibitors with PEO coatings,which can lead to improved performance of Mg alloy components in demanding environments.

Modeling asymmetric fracture mechanics of Mg alloy wire in drawing process

In this study,a numerical analysis was conducted on the ductile fracture of a 2-mm diameter Mg-1Zn-0.5Mn-0.5Sr-0.1Ca alloy wire during drawing.The hexagonally close-packed crystal structure of Mg alloys causes asymmetric fracture behavior,especially in the compression region.The aim of this study is to develop a comprehensive damage model for Mg alloy wire that accurately predicts ductile fracture,with a focus on the compression region.A novel experimental method was introduced to measure the ductile fracture of Mg alloy wires under different stress states.The wire drawing process was simulated using the Generalized Incremental Stress-State dependent damage(GISSMO)Model and the Semi-Analytical Model for Polymers(SAMP)model.The damage model's prediction and the experimental results were found to be in excellent agreement,especially in determining crack initiation.Computational analysis established a safe zone diagram for die angle and reduction ratio,and experimental validation confirmed the feasibility of this approach.The proposed damage model can provide a practical and reliable analysis for optimizing the drawing process of Mg alloy wire.