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Corrosion mechanism of Mg alloys involving elongated long-period stacking ordered phase and intragranular lamellar structure

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Journal of Materials Science & Technology 2023年第20期151卷 190-203页

作者： Jinshu Xie Jinghuai Zhang Zhi Zhang Zijian Yu Zhihao Xu Ru Wang Daqing Fang Xiaobo Zhang Xiaoru Zhang Ruizhi Wu Key Laboratory of Superlight Material and Surface Technology Ministry of EducationCollege of Materials Science and Chemical EngineeringHarbin Engineering UniversityHarbin 150001China Faculty of Materials and Manufacturing Beijing University of TechnologyBeijing 100124China State Key Laboratory for Mechanical Behavior of Materials Xi’an Jiaotong UniversityXi’an 710049China Jiangsu Key Laboratory of Advanced Structural Materials and Application Technology Nanjing Institute of TechnologyNanjing 211167China

It is a long-term challenge to further improve the corrosion resistance while ensuring the strength of magnesium(Mg)alloys.Revealing the effect of potential fluctuation on the micro-galvanic corrosion and the subsequent film formation is important for understanding the corrosion mechanism of Mg alloys with multiple strengthening phases/structures.Here,we prepared the high-strength Mg-14.4Er-1.44Zn-0.3Zr(wt.%)alloys containing hybrid structures,i.e.,elongated long-period stacking ordered(LPSO)blocks+intragranular stacking faults(SFs)/LPSO lamellae.The Mg alloy with elongated LPSO blocks and intragranular LPSO lamellae(EZ-500 alloy)obtains good corrosion resistance(2.2 mm y^(–1)),while the Mg alloy containing elongated LPSO blocks and intragranular SFs(EZ-400 alloy)shows a significantly higher corrosion rate(6.9 mm y^(–1)).The results of scanning Kelvin probe force microscopy(SKPFM)show the elongated LPSO blocks act as cathode phase(87 mV in EZ-400 alloy),and the SFs serve as the weak anode(30 mV in EZ-400 alloy),resulting in high potential fluctuation in EZ-400 alloy.On the contrary,both elongated blocks and intragranular lamellae are cathodic LPSO phase(67–69 mV)in EZ-500 alloy,leading to a lower potential fluctuation.Quasi in-situ atomic force microscope(AFM)observation indicates that high potential fluctuation would cause strong micro-galvanic corrosion,and subsequently leads to the failure in rapid formation of corrosion film,finally forming a loose and porous film,while relatively low potential fluctuation could result in more uniform corrosion mode and facilitate the rapid formation of protective film.Therefore,we propose that it is an effective way to develop high-strength corrosionresistant Mg alloys by controlling the potential fluctuation to form a“uniform potential”strengthening microstructure。

关键词： Mg alloys Stacking faults LPSO phase SKPFM Quasi in-situ AFM Corrosion behavior Potential fluctuation

Significant influence of trace Li on the mechanical properties, corrosion behavior, and antibacterial properties of biodegradable Zn–4Cu alloys

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Journal of Materials Science & Technology 2023年第20期151卷 245-257页

作者： Shiyu Huang Heng Liu Yanjing Su Lijie Qiao Yu Yan Beijing Advanced Innovation Center for Materials Genome Engineering Corrosion and Protection CenterInstitute for Advanced Materials and TechnologyUniversity of Science and TechnologyBeijing 100083China

In this work,trace Li was introduced to strengthen Zn–4Cu alloys.The results indicated that trace amounts of Li contributed to a significant increase in strength,resulting in an acceptable loss of elongation at fracture.Additionally,Li in the form of LiZn_(4) led to more intensive galvanic corrosion,which accelerated the early corrosion rate.The release of a large amount of Zn^(2+),caused by the addition of Li,affected the phase composition of the main Zn-containing corrosion products.Moreover,the inhibition effect of the alloy on Staphylococcus aureus(S.aureus)was enhanced by the addition of 0.02 wt.%Li.

关键词： Microalloying Zn-Cu alloy LiZn_(4)/Zn pairs Biodegradable mechanism SKPFM

Simultaneously improving mechanical and anti-corrosion properties of extruded Mg-Al dilute alloy via trace Er addition

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Journal of Materials Science & Technology 2023年第19期150卷 49-64页

作者： Zhi Zhang Jinshu Xie Jinghuai Zhang Hao Dong Shujuan Liu Xiaobo Zhang Jun Wang Ruizhi Wu Key Laboratory of Superlight Material and Surface Technology Ministry of EducationCollege of Materials Science and Chemical EngineeringHarbin Engineering UniversityHarbin 150001China School of Materials Science and Engineering Harbin Institute of TechnologyHarbin 150001China Jiangsu Key Laboratory of Advanced Structural Materials and Application Technology Nanjing Institute of TechnologyNanjing 211167China Ningbo Branch Ordnance Science Institute of ChinaNingbo 315103China

Simultaneously improving the mechanical properties and corrosion resistance of magnesium(Mg)alloys is a long-standing challenge to be solved in their engineering applications.In this work,we find that trace Er addition can improve the mechanical and anti-corrosion properties of Mg-1.4Al-0.4Mn-0.4Ca-0.3Er(wt%,AMXE)dilute alloy synergistically,especially reducing the corrosion rate(0.75 mm y-1)by one order of magnitude compared with the reference Mg-1.4Al-0.4Mn-0.4Ca(AMX)alloy and making it comparable to that of high-purity Mg.Adding trace Er reduces the dynamic recrystallization degree and increases the strengthening phase particles,which is mainly responsible for the increase of yield strength by 42 MPa.The addition of Er promotes the formation of much less noble Al8Mn4Er with effective Fe trapping ability and induces dislocation segregation,thus dramatically reducing micro-galvanic corrosion tendency.Meanwhile,Er addition promotes the formation of a more passivation and dense corrosion film.These two factors together lead to the extremely low corrosion rate of AMXE alloy.Our findings are expected to promote the development of low alloyed high performance Mg alloys.

关键词： Magnesium alloy Mechanics-corrosion synergy Rare earth element SKPFM

Developing new Mg alloy as potential bone repair material via constructing weak anode nano-lamellar structure

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Journal of Magnesium and Alloys 2023年第1期11卷 154-175页

作者： Jinshu Xie Lele Wang Jinghuai Zhang Liwei Lu Zhi Zhang Yuying He Ruizhi Wu Key Laboratory of Superlight Material and Surface Technology Ministry of EducationCollege of Materials Science and Chemical EngineeringHarbin Engineering UniversityHarbin150001China School of Materials Science and Engineering Hunan University of Science and TechnologyXiangtan411201China

The mechanics-corrosion and strength-ductility tradeoffs of magnesium(Mg)alloys have limited their applications in fields such as orthopedic implants.Herein,a fine-grain structure consisting of weak anodic nano-lamellar solute-enriched stacking faults(SESFs)with the average thickness of 8 nm and spacing of 16 nm is constructed in an as-extruded Mg96.9Y1.2Ho1.2Zn0.6Zr0.1(at.%)alloy,obtaining a high yield strength(YS)of 370 MPa,an excellent elongation(EL)of 17%,and a low corrosion rate of 0.30 mm y−1(close to that of high-pure Mg)in a uniform corrosion mode.Through scanning Kelvin probe force microscopy(SKPFM),one-dimensional nanostructured SESFs are identified as the weak anode(∼24 mV)for the first time.The excellent corrosion resistance is mainly related to the weak anodic nature of SESFs and their nano-lamellar structure,leading to the more uniform potential distribution to weaken galvanic corrosion and the release of abundant Y^(3+)/Ho^(3+)from SESFs to form a more protective film with an outer Ca_(10)(PO_(4))_(6)(OH)_(2)/Y_(2)O_(3)/Ho_(2)O_(3) layer(thickness percentage of this layer:72.45%).For comparison,the as-cast alloy containing block 18R long period stacking ordered(LPSO)phase and the heat-treated alloy with fine lamellar 18R-LPSO phase(thickness:80 nm,spacing:120 nm)are also studied,and the characteristics of SESFs and 18R-LPSO phase,such as the weak anode nature of the former and the cathode nature of the latter(37-90 mV),are distinguished under the same alloy composition.Ultimately,we put forward the idea of designing Mg alloys with high mechanical and anti-corrosion properties by constructing"homogeneous potential strengthening microstructure",such as the weak anode nano-lamellar SESFs structure.

关键词： Mg alloys Corrosion Solute-enriched stacking faults LPSO structure SKPFM Hydroxyapatite

Effect of Zn on mechanical and corrosion properties of Mg-Sc-Zn alloys

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Journal of Materials Science & Technology 2023年第27期158卷 31-42页

作者： Wenjun Ci Xianhua Chen Yue Sun Xu Dai Guanzheng Zhu Di Zhao Fusheng Pan International Joint Laboratory for Light Alloys(MOE) College of Materials Science and EngineeringChongqing UniversityChongqing 400045China National Engineering Research Center for Magnesium Alloys Chongqing UniversityChongqing 400045China State Key Laboratory of Power Transmission Equipment&System Security and New Technology Chongqing UniversityChongqing 400044China School of Mechanical Engineering Suzhou University of Science and TechnologySuzhou 215009China

The effect of different Zn concentrations(0 wt.%,1 wt.%,3 wt.%,and 6 wt.%)on the microstructure,cor-rosion property,and mechanical property of Mg-0.3Sc-x Zn(x=0 wt.%,1 wt.%,3 wt.%,and 6 wt.%)alloys was investigated.Here,MSZ1 alloy exhibits the highest corrosion resistance(0.194 mm/y)and appropriate mechanical properties with an ultimate tensile strength of 228 MPa and elongation of 19%.The superior corrosion resistance of Mg-0.3Sc-1Zn alloys is attributed to the homogeneous volta-potential distribution and the dense corrosion product film.With the increase in zinc content,the strength and plasticity of Mg-0.3Sc-x Zn alloys(x=0 wt.%,1 wt.%,3 wt.%,6 wt.%)improved to some extent.The precipitated ScZn phase plays the role of the second phase strengthening,which enables MSZ6 to obtain the maximum tensile strength.However,the ScZn phase with low volta potential intensifies the galvanic corrosion,re-sulting in the decline of the corrosion performance.

关键词： High corrosion resistance Mechanical performance Mg-Sc-Zn alloys SKPFM Corrosion product film

Distinct beneficial effect of Sn on the corrosion resistance of Cr-Mo low alloy steel

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Journal of Materials Science & Technology 2021年第22期81卷 175-189页

作者： Meihui Sun Xiaojia Yang Cuiwei Du Zhiyong Liu Yong Li Yumin Wu Hongyu San Xiandong Su Xiaogang Li Beijing Advanced Innovation Center for Materials Genome Engineering University of Science and Technology BeijingBeijing100083China National Materials Corrosion and Protection Scientific Data Center Institute of Advanced Materials and TechnologyBeijing100083China State Key Laboratory of Metal Material for Marine Equipment and Application Anshan114009China College of Materials Science and Engineering Chongqing UniversityChongqing 400045China

In this work,the beneficial effect of Sn addition on the corrosion resistance mechanism of Cr-Mo low alloy steel was studied.Results demonstrated that Sn improves the corrosion resistance of the steel matrix mainly by influencing the microstructural transformation.Sn addition and the synergistic effect of Sn,Cr,and Mo promote the formation of α-FeOOH,SnO_(2),SnO,Cr(OH)_(3),and molybdates,lead to the improved protection and stability of the rust layer.This synergistic effect also endows the inner rust layer with cation selectivity,preventing the further penetration of Cl-and inhibiting the localized corrosion of steel.

关键词： Sn addition Low alloy steel SKPFM TEM Corrosion resistance

(Gd,Y)相对GW103K时效合金局部腐蚀的影响

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材料研究学报 2019年第3期33卷 199-208页

作者：于爽贾瑞灵张函张伟郭锋内蒙古工业大学材料科学与工程学院内蒙古薄膜与涂层重点实验室呼和浩特010051 中国科学院金属研究所金属腐蚀与防护实验室沈阳110016

对Mg-10Gd-3Y-0.4Zr(GW103K)合金进行193 h时效处理,使用扫描电子显微镜(SEM)和透射电子显微镜(TEM)观测块状和链状相的微观结构和腐蚀形貌,使用扫描开尔文探针显微镜(SKPFM)测试块状相和链状相与基体之间的相对电势差,研究了这些相对GW... 详细信息

对Mg-10Gd-3Y-0.4Zr(GW103K)合金进行193 h时效处理,使用扫描电子显微镜(SEM)和透射电子显微镜(TEM)观测块状和链状相的微观结构和腐蚀形貌,使用扫描开尔文探针显微镜(SKPFM)测试块状相和链状相与基体之间的相对电势差,研究了这些相对GW103K合金局部腐蚀的影响。结果表明:分布在晶内和晶界的单独块状相为Mg2(Gd, Y)相,(Gd, Y)固溶体与Mg2(Gd, Y)相交替排列形成链状相。(Gd, Y)固溶体和Mg2(Gd, Y)相的相对电势均高于基体,与相邻基体形成微电池,(Gd, Y)固溶体和Mg2(Gd, Y)相作为阴极促进了周围基体的腐蚀。尽管(Gd,Y)固溶体与基体之间的相对电势差更大,但是与基体的相界面为共格界面,界面能低、化学稳定性高,因此对基体腐蚀没有更强烈的影响。

关键词：金属材料镁合金腐蚀微电偶 SKPFM (Gd,Y)相相对电势

Significantly improved corrosion resistance of Mg-15Gd-2Zn-0.39Zr alloys: Effect of heat-treatment

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Journal of Materials Science & Technology 2019年第8期35卷 1644-1654页

作者： Jing Liu Lixin Yang Chunyan Zhang Bo Zhang Tao Zhang Yang Li Kaiming Wu Fuhui Wang The State Key Laboratory of Refractories and Metallurgy Hubei Province Key Laboratory of Systems Science in Metallurgical Process International Research Institute for Steel Technology Wuhan University of Science and Technology 947 Heping Avenue Wuhan 430081 China Shenyang National Laboratory for Materials Science Institute of Metal Research Chinese Academy of Sciences Shenyang 110016 China Shenyang National Laboratory for Materials Science Northeastern University 3-11 Wenhua Road Shenyang 110819 China

The effects of heat-treatment on corrosion behavior of Mg-15Gd-2Zn-0.39Zr alloys were investigated through microstructure characterization, corrosion tests, and scanning Kelvin probe force microscope(SKPFM) analysis. In long-term corrosion experiments, the corrosion rates of Mg-Gd-Zn-Zr alloys were mainly determined by the effects of micro-galvanic corrosion. During heat-treatment, the β-(Mg,Zn)3Gd eutectic phase in as-cast alloys transformed into a long-period stacking ordered(LPSO) phase, coupled with the precipitation of small precipitates. As heat-treatment proceeded, the local potential and the volume fraction of the LPSO phases reduced gradually compared with the eutectic phase, which resulted in a remarkable decrease of the micro-galvanic effect between the second phase and Mg matrix. As a result, the corrosion resistance of heat-treated alloys improved significantly.

关键词： Mg-Gd-Zn-Zr alloy Corrosion behavior Heat-treatment LPSO phase SKPFM

Synergistic enhancement on mechanical properties and corrosion resistance of biodegradable Mg-Zn-Y alloy via V-microalloying

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Journal of Magnesium and Alloys 2024年第2期12卷 530-545页

作者： Jiaxin Zhang Xin Ding Ruirun Chen Wenchao Cao Jinshan Zhang Rui Zhao National Key Laboratory for Precision Hot Processing of Metals Harbin Institute of TechnologyNo.92West Dazhi StreetHarbinHeilongjiang 150001China College of Materials Science and Engineering Taiyuan University of TechnologyNo.79West Yingze StreetTaiyuanShanxi 030024China

For the sake of improving the mechanical properties and corrosion resistance of biodegradable Mg alloy synergistically,various content of element V(0,0.05,0.10,0.15,0.20 wt.%)are introduced into an Mg-Zn-Y alloy with long-period stacking ordered(LPSO)structure,and the effects of V on its microstructure,mechanical properties and corrosion resistance are investigated systematically.The results indicate that the grains are effectively refined by V addition,and the primaryα-Mg in Mg-Zn-Y-V0.1 alloy is most significantly refined,with grain size being decreased by 62%.The amount of 18R LPSO structure is increased owing to the V addition.The growth mode of the second phase(W-phase and 18R LPSO structure)is transformed to divorced growth pattern,which ascribes to the thermodynamic drive force of V to promote the nucleation of LPSO phase.Thus,18R LPSO structure presents a continuous distribution.Due to grains refinement and modification of second phase,the tensile strength and strain of alloys are both enhanced effectively.Especially,the ultimate tensile strength and the elongation of V0.1 alloy are 254 MPa and 15.26%,which are 41%and 61%higher than those of V-free alloy,respectively.Owing to the continuously distributed 18R LPSO structure with refined grains and stable product film,the weight loss and hydrogen evolution corrosion rates of V0.1 alloy are 7.1 and 6.2 mmy^(-1),respectively,which are 42.6%and 45.4%lower than those of V-free alloy.

关键词： Corrosion Mechanical property V-microalloying LPSO SKPFM