镁合金抗高温氧化机理研究进展
收稿日期: 2022-10-08
修回日期: 2022-11-23
网络出版日期: 2022-12-12
基金资助
国家科技重大专项项目No.J2019-Ⅷ-0003-0165(J2019-VIII-0003-0165)
Research Progress on the Mechanisms Controlling High-Temperature Oxidation Resistance of Mg Alloys
Received date: 2022-10-08
Revised date: 2022-11-23
Online published: 2022-12-12
Supported by
National Science and Technology Major Project of China(J2019-VIII-0003-0165)
本文简要回顾了国内外镁合金抗高温氧化机理的研究进展,归纳总结了纯Mg的高温氧化机理和镁合金高温氧化热力学与动力学及抗氧化机理,并探讨了先进表征技术在镁合金高温氧化研究中的潜在应用前景,最后展望了耐高温氧化镁合金的发展方向。主要观点如下:镁合金主要是通过形成具有一定厚度、连续且致密的氧化膜来抑制Mg蒸气向外扩散和O的内渗透;镁合金的高温氧化通常与第二相的热稳定性有密切关系;当微量合金元素不足以在表面生成相应氧化物时,可通过形成置换固溶体和反应性元素效应来提高保护作用;具有表面活性的元素会在合金表面富集并减小氧化物尺寸,从而增强氧化层;合金元素的选择性氧化与协同作用对镁合金的抗氧化性能至关重要;在镁合金中加入纳米或微型颗粒可通过减少特定的氧化区域来提高镁合金的高温抗氧化性。未来关于耐高温氧化镁合金的研究可基于以下方面继续深入:应用先进表征技术精准揭示镁合金抗氧化的机理和本质;建立合金元素与氧化膜晶粒尺寸和力学性能的内在关联;设计合理的多合金元素成分体系。
沈朝 , 王志鹏 , 胡波 , 李德江 , 曾小勤 , 丁文江 . 镁合金抗高温氧化机理研究进展[J]. 金属学报, 2023 , 59(3) : 371 -386 . DOI: 10.11900/0412.1961.2022.00495
This paper briefly reviews the progress on high-temperature oxidation mechanisms of pure Mg and Mg alloys, the thermodynamics and kinetics of high-temperature oxidation of Mg alloys, and the antioxidation mechanism of Mg alloys. The potential of applying advanced characterization techniques in studying the high-temperature oxidation of Mg alloys is envisaged. Finally, the development trends of the oxidation-resistant Mg alloy are also summarized. The main viewpoints are as follows: The protection of magnesium alloys at high temperatures is provided by the formation of a continuous, dense oxide scale that is a specific thickness and prevents the outward diffusion of magnesium vapor and the inward diffusion of oxygen; the oxidation resistance of Mg alloys is usually closely related to the thermal stability of the second phases; when the trace alloy elements are not enough to form the corresponding surface oxide scale, the oxidation resistance can be improved by creating a substitutional solid solution and using the reactive element effect; the size of the oxide grain size decreases and then enhances the oxidation resistance once the surface active elements is enriched on the surface of the alloys; the selective oxidation and synergistic effect of alloying elements are critical to the oxidation resistance of Mg alloys; the addition of nano or microparticles into the Mg alloys improve the high-temperature oxidation resistance of the Mg alloy by reducing the size of specific oxidation sensitive regions. In the future, the research on the high-temperature oxidation of Mg alloys can be based on the following aspects: Investigating the processes and nature of the oxidation resistance of Mg alloys using cutting-edge characterization techniques; constructing the underlying connections between the alloying elements and the oxide scale grain size and mechanical properties; designing and optimizing multi-alloying element composition systems.
| 1 | Davy H. Electro-chemical researches on the decomposition of the earths; with observations on the metals obtained from the alkaline earths, and on the amalgam procured from ammonia [J]. Philos. Trans. R. Soc. Lond., 1808, 98: 313 |
| 2 | Yang Y, Xiong X M, Chen J, et al. Research advances in magnesium and magnesium alloys worldwide in 2020 [J]. J. Magnes. Alloy., 2021, 9: 705 |
| 3 | Ding W J. Science and Technology of Magnesium Alloy [M]. Beijing: Science Press, 2007: 1 |
| 3 | 丁文江. 镁合金科学与技术 [M]. 北京: 科学出版社, 2007: 1 |
| 4 | Jeon J, Lee S, Kim B, et al. Effect of Sb and Sr addition on corrosion properties of Mg-5Al-2Si alloy [J]. J. Korean Inst. Met. Mater., 2008, 46: 304 |
| 5 | Jun J H, Kim J M, Park B K, et al. Effects of rare earth elements on microstructure and high temperature mechanical properties of ZC63 alloy [J]. J. Mater. Sci., 2005, 40: 2659 |
| 6 | Shin B, Kim Y, Bae D. Deformation behavior of a wrought Mg-Zn-RE alloy at the elevated temperatures [J]. J. Korean Inst. Met. Mater., 2008, 46: 1 |
| 7 | Toda-Caraballo I, Galindo-Nava E I, Rivera-Díaz-del-Castillo P E J. Understanding the factors influencing yield strength on Mg alloys [J]. Acta Mater., 2014, 75: 287 |
| 8 | Xu W Q, Birbilis N, Sha G, et al. A high-specific-strength and corrosion-resistant magnesium alloy [J]. Nat. Mater., 2015, 14: 1229 |
| 9 | Atrens A, Song G L, Liu M, et al. Review of recent developments in the field of magnesium corrosion [J]. Adv. Eng. Mater., 2015, 17: 400 |
| 10 | Abaspour S, Cáceres C H. Thermodynamics-based selection and design of creep-resistant cast Mg alloys [J]. Metall. Mater. Trans., 2015, 46A: 5972 |
| 11 | Mondal A K, Fechner D, Kumar S, et al. Interrupted creep behaviour of Mg alloys developed for powertrain applications [J]. Mater. Sci. Eng., 2010, A527: 2289 |
| 12 | Kondori B, Mahmudi R. Impression creep characteristics of a cast Mg alloy [J]. Metall. Mater. Trans., 2009, 40A: 2007 |
| 13 | Jin J, Li H, Li X H. Friction and wear behavior of micro arc oxidation coatings on magnesium alloy at high temperature [J]. Rare Met. Mater. Eng., 2017, 45: 1202 |
| 14 | Ming Y, You G Q, Yao F J, et al. Research progress on oxidation and oxidation mechanism of magnesium [J]. Mater. Rev., 2021, 35: 19134 |
| 14 | 明 玥, 游国强, 姚繁锦 等. 金属镁的氧化及氧化机理研究进展 [J]. 材料导报, 2021, 35: 19134 |
| 15 | Li D J, Cheng C L, Le Q C, et al. Progress on the oxidation mechanism of magnesium alloy [J]. Mater. Rev., 2023, 3: 1 |
| 15 | 李多娇, 程春龙, 乐启炽 等. 镁合金氧化机理研究进展 [J]. 材料导报, 2023, 3: 1 |
| 16 | Czerwinski F. Oxidation characteristics of magnesium alloys [J]. JOM, 2012, 64: 1477 |
| 17 | Czerwinski F. The reactive element effect on high-temperature oxidation of magnesium [J]. Int. Mater. Rev., 2015, 60: 264 |
| 18 | Pilling N B, Bedworth R E. The oxidation of metals at high temperatures [J]. J. Inst. Met., 1923, 29: 529 |
| 19 | Gulbransen E A. The oxidation and evaporation of magnesium at temperatures from 400oC to 500oC [J]. J. Electrochem. Soc., 1945, 87: 589 |
| 20 | Czerwinski F, Kedzierski Z. On the mechanism of microcrack formation in nanocrystalline Fe-Ni electrodeposits [J]. J. Mater. Sci., 1997, 32: 2957 |
| 21 | Jeurgens L P H, Vinodh M S, Mittemeijer E J. Initial oxide-film growth on Mg-based MgAl alloys at room temperature [J]. Acta Mater., 2008, 56: 4621 |
| 22 | Hakiki N E. Comparative study of structural and semiconducting properties of passive films and thermally grown oxides on AISI 304 stainless steel [J]. Corros. Sci., 2011, 53: 2688 |
| 23 | Smeltzer W W. The influence of short-circuit grain boundary diffusion on the growth of oxide layers on metals [J]. Mater. Sci. Forum, 1988, 29: 151 |
| 24 | Lea C, Molinari C. Magnesium diffusion, surface segregation and oxidation in Al-Mg alloys [J]. J. Mater. Sci., 1984, 19: 2336 |
| 25 | Krger F A. Physical chemistry of crystals [J]. Chem. Eng. News, 1965, 43: 88 |
| 26 | Smeltzer W W. Oxidation of an aluminum-3 per cent magnesium alloy in the temperature range 200-550oC [J]. J. Electrochem. Soc., 1958, 105: 67 |
| 27 | Finch G I, Quarrbell A G. The structure of magnesium, zinc and aluminium films [J]. Proc. Roy. Soc., 1933, 141A: 398 |
| 28 | Song X, Wang Z W, Zeng R C. Magnesium alloys: Composition, microstructure and ignition resistance [J]. Chin. J. Nonferrous Met., 2021, 31: 598 |
| 28 | 宋 祥, 王忠卫, 曾荣昌. 镁合金: 成分、组织与阻燃 [J]. 中国有色金属学报, 2021, 31: 598 |
| 29 | Wang X M, Zeng X Q, Zhou Y, et al. Early oxidation behaviors of Mg-Y alloys at high temperatures [J]. J. Alloys Compd., 2008, 460: 368 |
| 30 | Yu X W, Jiang B, He J J, et al. Effect of Zn addition on the oxidation property of Mg-Y alloy at high temperatures [J]. J. Alloys Compd., 2016, 687: 252 |
| 31 | Wu J J, Yuan Y, Yang L, et al. The oxidation behavior of Mg-Er binary alloys at 500oC [J]. Corros. Sci., 2022, 195: 109961 |
| 32 | Aydin D S, Bayindir Z, Pekguleryuz M O. The effect of strontium (Sr) on the ignition temperature of magnesium (Mg): A look at the pre-ignition stage of Mg-6 wt% Sr [J]. J. Mater. Sci., 2013, 48: 8117 |
| 33 | Lee D B. High temperature oxidation of AZ31 + 0.3 wt.%Ca and AZ31 + 0.3 wt.%CaO magnesium alloys [J]. Corros. Sci., 2013, 70: 243 |
| 34 | Ming Y, You G Q, Yao F J, et al. High-temperature oxidation of Mg-Ca alloy: Experimentation and density functional theory [J]. Corros. Sci., 2022, 196: 110046 |
| 35 | Czerwinski F. The early stage oxidation and evaporation of Mg-9%Al-1%Zn alloy [J]. Corros. Sci., 2004, 46: 377 |
| 36 | Tan Q Y, Mo N, Lin C L, et al. Improved oxidation resistance of Mg-9Al-1Zn alloy microalloyed with 60 wt ppm Be attributed to the formation of a more protective (Mg, Be)O surface oxide [J]. Corros. Sci., 2018, 132: 272 |
| 37 | Tan Q Y, Atrens A, Mo N, et al. Oxidation of magnesium alloys at elevated temperatures in air: A review [J]. Corros. Sci., 2016, 112: 734 |
| 38 | Tan Q Y, Mo N, Jiang B, et al. Combined influence of Be and Ca on improving the high-temperature oxidation resistance of the magnesium alloy Mg-9Al-1Zn [J]. Corros. Sci., 2017, 122: 1 |
| 39 | Wang X M, Zeng X Q, Wu G S, et al. Surface oxidation behavior of MgNd alloys [J]. Appl. Surf. Sci., 2007, 253: 9017 |
| 40 | Guan M, Hao W X, Fan J F. High temperature oxidation behavior of ignition-proof Mg-Y-Ce alloys [J]. Rare Met. Mater. Eng., 2010, 39: 1375 |
| 40 | 关 明, 郝维新, 樊建锋. Mg-Y-Ce稀土阻燃镁合金的高温氧化行为研究 [J]. 稀有金属材料与工程, 2010, 39: 1375 |
| 41 | Yu X W, Shen S J, Jiang B, et al. The effect of the existing state of Y on high temperature oxidation properties of magnesium alloys [J]. Appl. Surf. Sci., 2016, 370: 357 |
| 42 | Tan Q Y, Mo N, Lin C L, et al. Generalisation of the oxide reinforcement model for the high oxidation resistance of some Mg alloys micro-alloyed with Be [J]. Corros. Sci., 2019, 147: 357 |
| 43 | Tan Q Y, Yin Y, Mo N, et al. Recent understanding of the oxidation and burning of magnesium alloys [J]. Surf. Innov., 2019, 7: 71 |
| 44 | Cheng C L, Li X Q, Le Q C, et al. Effect of REs (Y, Nd) addition on high temperature oxidation kinetics, oxide layer characteristic and activation energy of AZ80 alloy [J]. J. Magnes. Alloy., 2020, 8: 1281 |
| 45 | Barrena M I, de Salazar J M G, Matesanz L, et al. Effect of heat treatments on oxidation kinetics in AZ91 and AM60 magnesium alloys [J]. Mater. Charact., 2011, 62: 982 |
| 46 | Inoue S I, Yamasaki M, Kawamura Y. Classification of high-temperature oxidation behavior of Mg-1 at% X binary alloys and application of proposed taxonomy to nonflammable multicomponent Mg alloys [J]. Corros. Sci., 2020, 174: 108858 |
| 47 | Feng Z X, Shi Q N, Wang X Q, et al. Effect of Sr and Ca compound alloying on oxidation weight gain of the AZ31 magnesium alloy [J]. J. Funct. Mater., 2016, 47: 8124 |
| 47 | 冯中学, 史庆南, 王效琪 等. Sr、Ca复合添加对AZ31镁合金氧化增重的影响 [J]. 功能材料, 2016, 47: 8124 |
| 48 | Yuan C M, Huang D Z, Li C, et al. Ignition behavior of magnesium powder layers on a plate heated at constant temperature [J]. J. Hazard. Mater., 2013, 246-247: 283 |
| 49 | Südholz A D, Birbilis N, Bettles C J, et al. Corrosion behaviour of Mg-alloy AZ91E with atypical alloying additions [J]. J. Alloys Compd., 2007, 471: 109 |
| 50 | Stumphy B, Mudryk Y, Russell A, et al. Oxidation resistance of B2 rare earth-magnesium intermetallic compounds [J]. J. Alloys Compd., 2008, 460: 363 |
| 51 | Emuna M, Greenberg Y, Hevroni R, et al. Phase diagrams of binary alloys under pressure [J]. J. Alloys Compd., 2016, 687: 360 |
| 52 | Arrabal R, Pardo A, Merino M C, et al. Oxidation behavior of AZ91D magnesium alloy containing Nd or Gd [J]. Oxid. Met., 2011, 76: 433 |
| 53 | Zhang M X, Kelly P M. Surface alloying of AZ91D alloy by diffusion coating [J]. J. Mater. Res., 2002, 17: 2477 |
| 54 | Shih T S, Liu J B, Wei P S. Oxide films on magnesium and magnesium alloys [J]. Mater. Chem. Phys., 2007, 104: 497 |
| 55 | Pan N, Wei Y H, Hou L F, et al. Oxidation process of AZ61 magnesium alloy at high temperature [J]. Trans. Mater. Heat Treat., 2013, 34(3): 67 |
| 55 | 潘 娜, 卫英慧, 侯利锋 等. AZ61镁合金高温氧化过程 [J]. 材料热处理学报, 2013, 34(3): 67 |
| 56 | Min X G, Du W W, Xue F, et al. Analysis of EET on Ca increasing the melting point of Mg17Al12 phase [J]. Chin. Sci. Bull., 2002, 47: 109 |
| 56 | 闵学刚, 杜温文, 薛 烽 等. Ca提高Mg17Al12相熔点的现象及EET理论分析 [J]. 科学通报, 2002, 47: 109 |
| 57 | Hu C K, Zhao Q, Wang Y B, et al. Heat treatment of Mg-10Gd-3Y-Zr magnesium alloy [J]. Heat Treat. Met., 2018, 43(9): 94 |
| 57 | 胡传凯, 赵 强, 王艳彬 等. Mg-10Gd-3Y-Zr镁合金的热处理工艺 [J]. 金属热处理, 2018, 43(9): 94 |
| 58 | Youdelis W V, Yang C S. Beryllium-enhanced grain refinement of aluminium-titanium alloys [J]. Met. Sci., 1982, 16: 275 |
| 59 | Silversmith D J, Averbach B L. Pressure dependence of the elastic constants of beryllium and beryllium-copper alloys [J]. Phys. Rev., 1970, 1B: 567 |
| 60 | Zhao H J, Zhang Y H, Kang Y L, et al. Oxidization thermo-dynamics of ignition-proof element and oxides properties in magnesium alloy [J]. Spec. Cast. Nonferrous Alloys, 2006, 26: 340 |
| 60 | 赵鸿金, 张迎晖, 康永林 等. 镁合金阻燃元素氧化热力学及氧化物物性分析 [J]. 特种铸造及有色合金, 2006, 26: 340 |
| 61 | Balch O K, O'Dwyer J G, Davis G R, et al. Plasticity and damage in aluminum syntactic foams deformed under dynamic and quasi-static conditions [J]. Mater. Sci. Eng., 2005, A391: 408 |
| 62 | Foerster G. HiLoN: A new approach to magnesium die casting [J]. Adv. Mater. Process., 1998, 154: 79 |
| 63 | Wikle K G. Improving aluminum castings with beryllium [J]. AFS Trans., 1978, 6: 119 |
| 64 | Pint B A. Experimental observations in support of the dynamic-segregation theory to explain the reactive-element effect [J]. Oxid. Met., 1996, 45: 1 |
| 65 | Kiejna A. Comment on the surface segregation in alkali-metal alloys [J]. J. Phys. Condens. Matter., 1990, 2: 6331 |
| 66 | Aydin D S, Bayindir Z, Pekguleryuz M O. High temperature oxidation behavior of hypoeutectic Mg-Sr binary alloys: The Role of the two-phase microstructure and the surface activity of Sr [J]. Adv. Eng. Mater., 2015, 17: 697 |
| 67 | Luo L L, Kang Y H, Yang J C, et al. Nucleation and growth of oxide islands during the initial-stage oxidation of (100)Cu-Pt alloys [J]. J. Appl. Phys., 2015, 117: 065305 |
| 68 | Diawara B, Beh Y A, Marcus P. Nucleation and growth of oxide layers on stainless steels (FeCr) using a virtual oxide layer model [J]. J. Phys. Chem., 2010, 114C: 19299 |
| 69 | Cai Y, Yan H, Zhu M Y, et al. High-temperature oxidation behavior and corrosion behavior of high strength Mg-xGd alloys with high Gd content [J]. Corros. Sci., 2021, 193: 109872 |
| 70 | Rokhlin L L. Magnesium Alloys Containing Rare Earth Metals [M]. London: CRC Press, 2003: 10 |
| 71 | Cox E G. Structural inorganic chemistry [J]. Nature, 1946, 157: 386 |
| 72 | Huang Y B, Chung I S, You B S, et al. Effect of Be addition on the oxidation behavior of Mg-Ca alloys at elevated temperature [J]. Met. Mater. Int., 2004, 10: 7 |
| 73 | Van Orman J A, Crispin K L. Diffusion in oxides [J]. Rev. Mineral. Geochem., 2010, 72: 757 |
| 74 | Zeng X Q, Wang Q D, Lü Y Z, et al. Behavior of surface oxidation on molten Mg-9Al-0.5Zn-0.3Be alloy [J]. Mater. Sci. Eng., 2001, A301: 154 |
| 75 | Zeng X Q, Wang Q D, Lü Y Z, et al. Study on ignition proof magnesium alloy with beryllium and rare earth additions [J]. Scr. Mater., 2000, 43: 403 |
| 76 | Tan Q Y, Mo N, Jiang B, et al. Oxidation resistance of Mg-9Al-1Zn alloys micro-alloyed with Be [J]. Scr. Mater., 2016, 115: 38 |
| 77 | Cao P, Qian M, Stjohn D H. Grain coarsening of magnesium alloys by beryllium [J]. Scr. Mater., 2004, 51: 647 |
| 78 | Cao P, Qian M, Stjohn D H. Mechanism for grain refinement of magnesium alloys by superheating [J]. Scr. Mater., 2007, 56: 633 |
| 79 | Fan J F, Yang G C, Zhou Y H, et al. Selective oxidation and the third-element effect on the oxidation of Mg-Y alloys at high temperatures [J]. Metall. Mater. Trans., 2009, 40A: 2184 |
| 80 | Adachi G Y, Imanaka N. The binary rare earth oxides [J]. Chem. Rev., 1998, 98: 1479 |
| 81 | Li M S. Corrosion of Metals at High Temperature [M]. Beijing: Metallurgical Industry Press, 2001: 187 |
| 81 | 李美栓. 金属的高温腐蚀 [M]. 北京: 冶金工业出版社, 2001: 187 |
| 82 | Nguyen Q B, Gupta M, Srivatsan T S. On the role of nano-alumina particulate reinforcements in enhancing the oxidation resistance of magnesium alloy AZ31B [J]. Mater. Sci. Eng., 2009, A500: 233 |
| 83 | Shao Y H, Wang J L, Zhang W, et al. High temperature oxidation behavior of a heat resistant magnesium alloy Mg-14Gd-2.3Zn-Zr [J]. J. Chin. Soc. Corros. Prot., 2022, 42: 73 |
| 83 | 邵银华, 王金龙, 张 伟 等. 耐热镁合金Mg-14Gd-2.3Zn-Zr的高温氧化行为研究 [J]. 中国腐蚀与防护学报, 2022, 42: 73 |
| 84 | Nguyen T D, Lee D B. Oxidation of AM60B Mg alloys containing dispersed SiC particles in air at temperatures between 400 and 550oC [J]. Oxid. Met., 2010, 73: 183 |
| 85 | Wang X J, Hu X S, Wu K, et al. Hot deformation behavior of SiCp/AZ91 magnesium matrix composite fabricated by stir casting [J]. Mater. Sci. Eng., 2008, A492: 481 |
| 86 | Li J Q, Wang L, Cheng H W, et al. Synthesis and compressive deformation of rapidly solidified magnesium alloy and composites reinforced by SiCp [J]. Mater. Sci. Eng., 2008, A474: 24 |
| 87 | Yang W, Weatherly G C, McComb D W, et al. The structure of SiC-reinforced Mg casting alloys [J]. J. Microsc., 1997, 185: 292 |
| 88 | Shen Z, Chen K, Yu H B, et al. New insights into the oxidation mechanisms of a ferritic-martensitic steel in high-temperature steam [J]. Acta Mater., 2020, 194: 522 |
| 89 | Shen Z, Tweddle D, Yu H B, et al. Microstructural understanding of the oxidation of an austenitic stainless steel in high-temperature steam through advanced characterization [J]. Acta Mater., 2020, 194: 321 |
| 90 | Chen K, Zhang L F, Shen Z. Understanding the surface oxide evolution of T91 ferritic-martensitic steel in supercritical water through advanced characterization [J]. Acta Mater., 2020, 194: 156 |
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