基于卤素效应的阳极氧化技术提高Ti48Al5Nb合金抗高温氧化性能
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摘要
采用电化学阳极氧化技术在含NH_4F的乙二醇电解液中对Ti48Al5Nb合金进行阳极氧化处理,以获得富铝含氟阳极氧化膜。研究了阳极氧化处理对Ti48Al5Nb合金在1000℃空气中的氧化行为及氧化膜组成和结构的影响。结果表明:阳极氧化处理的Ti48Al5Nb合金经高温氧化后表面可形成连续、致密的Al_2O_3氧化膜,且氧化膜与基体具有良好结合力,有效阻止了氧向内扩散,进而显著提高了合金的抗高温氧化性能。经1000℃氧化100 h后,阳极氧化试样增重由未经阳极氧化处理试样的26.73 mg/cm~2降至1.18 mg/cm~2。同时,阳极氧化处理改变了合金的氧化机制,抑制了氧化膜/基体界面处富Nb层的出现。阳极氧化提高Ti48Al5Nb合金抗高温氧化性能是由于氧化膜中F在高温氧化过程中表现出的"卤素效应"所致。
Ti48Al5Nb alloy was electrochemically anodized in electrolyte of ethylene glycol with NH_4F to prepare anodic films containing fluorine and aluminum. The influence of anodization treatment on the oxidation behavior, the composition and structure of the oxide scale of the anodized Ti48Al5Nb alloy were then characterized. Results shown that a continuous and dense Al_2O_3 oxide scale will generate on the anodized Ti48Al5Nb alloy after high temperature oxidation. And this oxide scale has good adhesion with the substrate, therefore can efficiently prevent the inward diffusion of oxygen, resulting the enhanced high temperature oxidation resistance. After oxidation at 1000 ℃ for 100 h, the weight gain of the anodized Ti48Al5Nb alloy was dramatically decreased from 26.73 mg·cm~(-2) for the bare Ti48Al5Nb alloy to 1.18 mg·cm~(-2). Moreover, it is shown that anodization also changes the oxidation mechanism, leading to the disappearance of the Nb-enriched layer at the interface between the oxide scale and substrate.The enhanced high temperature oxidation of the anodized Ti48Al5Nb is derived from the halogen effect based on the fluorine compounds existed in the anodized film.
Ti48Al5Nb alloy was electrochemically anodized in electrolyte of ethylene glycol with NH_4F to prepare anodic films containing fluorine and aluminum. The influence of anodization treatment on the oxidation behavior, the composition and structure of the oxide scale of the anodized Ti48Al5Nb alloy were then characterized. Results shown that a continuous and dense Al_2O_3 oxide scale will generate on the anodized Ti48Al5Nb alloy after high temperature oxidation. And this oxide scale has good adhesion with the substrate, therefore can efficiently prevent the inward diffusion of oxygen, resulting the enhanced high temperature oxidation resistance. After oxidation at 1000 ℃ for 100 h, the weight gain of the anodized Ti48Al5Nb alloy was dramatically decreased from 26.73 mg·cm~(-2) for the bare Ti48Al5Nb alloy to 1.18 mg·cm~(-2). Moreover, it is shown that anodization also changes the oxidation mechanism, leading to the disappearance of the Nb-enriched layer at the interface between the oxide scale and substrate.The enhanced high temperature oxidation of the anodized Ti48Al5Nb is derived from the halogen effect based on the fluorine compounds existed in the anodized film.
引文
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[27]Norasetthekul S,Park P Y,Baik K H,et al.Dry etch chemistries for TiO2thin films[J].Appl.Surf.Sci.,2001,185:27
[2]Zhang M M,Xin L,Ding X Y,et al.Corrosion resistance of alternately multilayered coating Ti/TiAlN on Ti-alloy Ti-6Al-4V beneath a solid NaCl film in atmosphere of water vapor and oxygen at600°C[J].J.Chin.Soc.Corros.Prot.,2017,37:29(张明明,辛丽,丁学勇等.600℃/NaCl-H2O-O2协同环境中Ti/TiAlN多层涂层的耐蚀行为[J].中国腐蚀与防护学报,2017,37:29)
[3]Peng X M,Xia C Q,Wang Z H,et al.Development of high temperature oxidation and protection of TiAl-based alloy[J].Chin.J.Nonferrous Met.,2010,20:1116(彭小敏,夏长清,王志辉等.TiAl基合金高温氧化及防护的研究进展[J].中国有色金属学报,2010,20:1116)
[4]Pflumm R,Friedle S,Schütze M.Oxidation protection ofγ-TiAlbased alloys-A review[J].Intermetallics,2015,56:1
[5]Dai J J,Zhu J Y,Chen C Z,et al.High temperature oxidation behavior and research status of modifications on improving high temperature oxidation resistance of titanium alloys and titanium aluminides:A review[J].J.Alloy.Compd.,2016,685:784
[6]Pflumm R,Donchev A,Mayer S,et al.High-temperature oxidation behavior of multi-phase Mo-containingγ-TiAl-based alloys[J].Intermetallics,2014,53:45
[7]Wu Y,Hagihara K,Umakoshi Y.Influence of Y-addition on the oxidation behavior of Al-richγ-TiAl alloys[J].Intermetallics,2004,12:519
[8]Taniguchi S,Kuwayama T,Zhu Y C,et al.Influence of silicon ion implantation and post-implantation annealing on the oxidation behaviour of TiAl under thermal cycle conditions[J].Mater.Sci.Eng.,2000,A277:229
[9]Li X Y,Taniguchi S,Matsunaga Y,et al.Influence of siliconizing on the oxidation behavior of aγ-TiAl based alloy[J].Intermetallics,2003,11:143
[10]Shida Y,Anada H.The effect of various ternary additives on the oxidation behavior of Ti Al in high-temperature air[J].Oxid.Met.,1996,45:197
[11]Shen Y,Ding X F,Wang F G,et al.High-temperature oxidation resistance of high-Nb Ti Al-based alloy[J].J.Chin.Soc.Corros.Prot.,2004,24:203(沈勇,丁晓非,王富岗等.高铌TiAl基合金高温抗氧化性能研究[J].中国腐蚀与防护学报,2004,24:203)
[12]Lin J P,Zhao L L,Li G Y,et al.Effect of Nb on oxidation behavior of high Nb containing TiAl alloys[J].Intermetallics,2011,19:131
[13]Varma S K,Chan A,Mahapatra B N.Static and cyclic oxidation of Ti-44Al and Ti-44Al-x Nb alloys[J].Oxid.Met.,2001,55:423
[14]Jiang H R,Hirohasi M,Lu Y,et al.Effect of Nb on the high temperature oxidation of Ti-(0-50 at.%)Al[J].Scr.Mater.,2002,46:639
[15]Wang D S,Tian Z J,Chen Z Y,et al.High-temperature oxidation resistance coatings on Ti Al alloy surface[J].J.Chin.Soc.Corros.Prot.,2009,29:1(王东生,田宗军,陈志勇等.TiAl合金表面抗高温氧化涂层研究[J].中国腐蚀与防护学报,2009,29:1)
[16]Shen M L,Zhu S L,Wang F H.Formation kinetics of multi-layered interfacial zone betweenγ-TiAl and glass-ceramic coatings via interfacial reactions at 1000°C[J].Corros.Sci.,2015,91:341
[17]Schütze M.The role of surface protection for high-temperature performance of Ti Al alloys[J].JOM,2017,69:2602
[18]Friedle S,Pflumm R,Seyeux A,et al.ToF-SIMS study on the initial stages of the halogen effect in the oxidation of TiAl alloys[J].Oxid.Met.,2018,89:123
[19]Friedle S,Laska N,Braun R,et al.Oxidation behaviour of a fluorinated beta-stabilizedγ-TiAl alloy with thermal barrier coatings in H2O-and SO2-containing atmospheres[J].Corros.Sci.,2015,92:280
[20]Donchev A,Richter E,Schütze M,et al.Improving the oxidation resistance of TiAl-alloys with fluorine[J].J.Alloy.Compd.,2008,452:7
[21]Schütze M,Schumacher G,Dettenwanger F,et al.The halogen effect in the oxidation of intermetallic titanium aluminides[J].Corros.Sci.,2002,44:303
[22]Donchev A,Gleeson B,Schütze M.Thermodynamic considerations of the beneficial effect of halogens on the oxidation resistance of TiAl-based alloys[J].Intermetallics,2003,11:387
[23]Mo M H,Wu L K,Cao H Z,et al.Improvement of the high temperature oxidation resistance of Ti-50Al at 1000℃by anodizing in ethylene glycol/BmimPF6 solution[J].Surf.Coat.Technol.,2016,286:215
[24]Mo M H,Wu L K,Cao H Z,et al.High temperature oxidation behavior and anti-oxidation mechanism of Ti-50Al anodized in ionic liquid[J].Surf.Coat.Technol.,2016,307:190
[25]Mo M H,Wu L K,Cao H Z,et al.Halogen effect for improving high temperature oxidation resistance of Ti-50Al by anodization[J].Appl.Surf.Sci.,2017,407:246
[26]Wu L K,Xia J J,Cao H Z,et al.Improving the high-temperature oxidation resistance of TiAl alloy by anodizing in Methanol/NaFsolution[J].Oxid.Met.,2018,90:617
[27]Norasetthekul S,Park P Y,Baik K H,et al.Dry etch chemistries for TiO2thin films[J].Appl.Surf.Sci.,2001,185:27