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

Journal of Magnesium and alloys 2024年第2期12卷 586-607页

作者： Muhammad Ali Khan Ananda Repycha Safira Mohammad Aadil Mosab Kaseem Corrosion and Electrochemistry Laboratory Department of Nanotechnology and Advanced Materials EngineeringSejong UniversitySeoul 05006Republic of Korea

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.

关键词： mg alloy Layered double hydroxide Metal-organic frameworks Corrosion DFT

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

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Journal of Magnesium and alloys 2024年第1期12卷 332-344页

作者： Z.Y.Xue X.J.Li J.H.Chu M.M.Li D.N.Zou L.B.Tong School of Metallurgical Engineering Xi’an University of Architecture and TechnologyXi’an 710055China State Key Laboratory of Advanced Design and Manufacturing for Vehicle Body Hunan UniversityChangsha 410082China

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.

关键词： mg alloy Functionalized graphene Epoxy coating Corrosion/wear resistance Blocking layer

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Strategy for suppressing abnormal grain growth of ZK60 mg alloy during solution by pre-compression:A quasi-in-situ study

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Journal of Materials Science & Technology 2024年第4期171卷 115-128页

作者： Zhenxu Wang Liang Chen Jianwei Tang Cunsheng Zhang Guoqun Zhao Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials(Ministry of Education) Shandong UniversityJinanShandong 250061China Department of Mechanical Engineering Kyushu UniversityFukuoka 819-0395Japan

Abnormal grain growth(AGG)easily takes place in mg alloys during high-temperature solutions,result-ing in deterioration of mechanical properties.Hence,the compression prior to solution(pre-compression)was conducted to suppress AGG,and the microstructure evolution as well as suppressing mechanisms was investigated based on quasi-in-situ analysis.After compression along the transverse direction,//ED grains preferentially nucleated and rapidly grew up,and the initial//ED texture was weakened.Two grain growth modes of heat-induced and strain-induced grain boundary migrations were found.The former was attributed to the high interfacial energy of grain boundaries with large curvature.The latter consumed the adjacent grains with high storage energy,forming abnormal grains with irregular shapes.The compression with a reduction>6%could obviously suppress AGG.The suppressing effects were mainly attributed to weakening the size advantage of//ED grains,increasing nucleation,reducing grain boundary character distribution,and redistributing storage energy distribution.After 12%compression along the transverse direction,30°misorientation of//ED grains and high energy grain boundaries were reduced.The{10-12}tensile twins and{10-15}high index twins induced by com-pression increased the nucleation of static recrystallization.Beside,compression introduces high-density dislocations,which also contributed to suppressing AGG behavior during solution.

关键词： Quasi-in-situ analysis mg alloy Abnormal grain growth Compression Microstructure

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

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Journal of Magnesium and alloys 2024年第2期12卷 573-585页

作者： Mengyao Liu Yabo Zhang Qingyuan Zhang Yan Wang Di Mei Yufeng Sun Liguo Wang Shijie Zhu Shaokang Guan School of Materials Science and Engineering Zhengzhou UniversityZhengzhou 450001China Henan Key Laboratory of Advanced Magnesium alloys Zhengzhou 450002China Key Laboratory of Advanced Materials Processing&Mold Ministry of Education Zhengzhou 450002China

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.

关键词： mg alloy Microtubes Degradation behavior Radial compressive stress Dynamic conditions

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Modeling asymmetric fracture mechanics of mg alloy wire in drawing process

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Journal of Magnesium and alloys 2024年第5期12卷 2057-2069页

作者： Sunghoon Choi Jongwon Shin Joung Sik Suh Dongchoul Kim Department of Mechanical Engineering Sogang University Advanced Metals Division Korea Institute of Materials Science

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.

关键词： mg alloy Wire drawing Finite element method Damage model Safe zone diagram

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Antibacterial HA-coatings on bioresorbable mg alloy

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Journal of Magnesium and alloys 2024年第5期12卷 1965-1985页

作者： K.V.Nadaraia D.V.Mashtalyar M.A.Piatkova A.I.Pleshkova I.M.Imshinetskiy M.S.Gerasimenko E.A.Belov V.V.Kumeiko D.N.Kozyrev K.A.Fomenko V.V.Mostovaya B.R.Torpanov A.R.Biktimirov I.S.Osmushko S.L.Sinebryukhov S.V.Gnedenkov Institute of Chemistry FEB RAS Far Eastern Federal University A.V.Zhirmunsky National Scientific Center of Marine Biology FEB RAS Regional Clinical Dermatovenerological Dispensary NMIC “Treatment and Rehabilitation Center”

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.

关键词： Bioactive coatings Biocompatibility mg alloy Plasma electrolytic oxidation Hydroxyapatite Vancomycin

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

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Journal of Magnesium and alloys 2024年第3期12卷 1021-1025页

作者： Jing Xu Bo Guan Yunchang Xin Guangjie Huang Peidong Wu Qing Liu International Joint Laboratory for Light alloys College of Materials Science and EngineeringChongqing UniversityChongqing 400030China Key Laboratory for Light-weight Materials Nanjing Tech UniversityNanjing 210009China Department of Mechanical Engineering McMaster UniversityHamiltonON L8S 4L7Canada

The high ductility of mg-Li alloy has been mainly ascribed to a high activity of pyramidalslip to accommodate plastic strain.In the present study,however,a quantitative analysis reveals that Li-addition can only slightly stimulate the activation of pyramidalslip 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 pyramidalslip 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.

关键词： mg alloy Plasticity Plastic deformation Slip Twinning.

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

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Journal of Magnesium and alloys 2024年第4期12卷 1529-1539页

作者： Bin-Jiang Lv Sen Wang Fu-Hao Gao Ning Cui Yi-Nan Li Tie-Wei Xu Feng Guo School of Mechanical and Automotive Engineering Qingdao University of Technology266520China Key Lab of industrial Fluid Energy Conservation and Pollution Control Qingdao University of Technology266520China

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°boundaries formed due to twin–twin intersections under different strain rates.Isolated twin variants with 60°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°boundaries transformed into new grains via dynamic recrystallization.

关键词： mg alloy Twin-twin intersection Lattice rotation Dynamic recrystallization

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

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Journal of Magnesium and alloys 2024年第5期12卷 1841-1853页

作者： M.Lv H.L.Ge Q.Q.Jin X.H.Shao Y.T.Zhou B.Zhang X.L.Ma Shenyang National Laboratory for Materials Science Institute of Metal Research Chinese Academy of Sciences School of Materials Science and Engineering University of Science and Technology of China Materials Science and Engineering Research Center Guangxi University of Science and Technology

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.

关键词： mg alloy Electron beam irradiation Hardening Precipitates In-situ TEM

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Simultaneously improving mechanical properties and corrosion resistance of as-cast AZ91 mg alloy by ultrasonic surface rolling

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International Journal of Minerals,Metallurgy and Materials 2022年第8期29卷 1551-1558页

作者： Jing Han Cong Wang Yuanming Song Zhiyuan Liu Jiapeng Sun Jiyun Zhao School of Mechanical and Electrical Engineering China University of Mining and TechnologyXuzhou 221116China Jiangsu Engineering Technology Research Center on Intelligent Equipment for Fully Mining and Excavating Xuzhou 221116China College of Mechanics and Materials Hohai UniversityNanjing 211100China

mg alloy casting parts commonly suffer from drawbacks of low surface properties,high susceptibility to corrosion,unsatisfactory absolute strength,and poor ductility,which seriously limit their wide application.Here,a surface nanocrystallization technique,i.e.,ultrasonic surface rolling(USR),was applied on an as-cast AZ91 mg alloy sheet to improve its corrosion resistance and mechanical properties.The USR produces double smooth surfaces with Ra 0.036μm and gradient nanostructured surface layers on the sheet.Due to this special microstructure modification,the USR sheet exhibits 55%and 50%improvements in yield strength and ultimate tensile strength without visibly sacrificed ductility comparable to its untreated counterpart,as well as a 24%improvement in surface hardness.The USR sheet also shows good corrosion resistance in 3.5wt%NaCl aqueous solution.The corrosion current density of the USR sheet reduces by 63%after immersion for 1 h,and 25%after immersion for 24 h compared to that of the untreated counterpart.The enhanced strength and hardness are mainly related to the gradient nanostructure.The improved corrosion resistance is mainly ascribed to the decreased surface roughness,nanostructured surface,and residual compressive stress.The present results state that USR is an effective and attractive method to improve the multiple properties of mg alloy cast-ing parts,and thus can be used as an additional and last working procedure to achieve high-performance mg alloy casting parts.

关键词： mg alloy ultrasonic surface rolling surface nanocrystallization microstructure strength corrosion

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