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Forming efficiency of porous anodic oxide and formation mechanism of nanopores

Zhu Xu-Fei Han Hua Song Ye Ma Hong-Tu Qi Wei-Xing Lu Chao Xu Chen

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Forming efficiency of porous anodic oxide and formation mechanism of nanopores

Zhu Xu-Fei, Han Hua, Song Ye, Ma Hong-Tu, Qi Wei-Xing, Lu Chao, Xu Chen
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  • Porous anodic alumina (PAA) and porous anodic TiO2 nanotubes have received considerable attention because of their applications in a number of fields. The formation mechanisms of nanopores and nanotubes in these porous anodic oxides, however, have remained unclear until now. The interactions between porous structural features and current-time transients in anodizing process cannot be successfully explained. Based on the mechanism of dielectric breakdown of the compact anodic alumina (CAA), the differences and internal relations in their forming processes between CAA and PAA are contrasted in detail. From this innovative standpoint, according to the divergence of PAA and CAA in their current-time curves (or voltage-time curves), two essential causes which induce the decrease of the forming efficiency of oxide in the anodizing process, that is, the generation of the electronic current and the oxygen evolution, are presented in the paper. The evidences of the round hollows within the CAA films, show that the regularly embryo pores result from the oxygen bubbles. According to the aluminum anodizing in the mixed-electrolyte, the results show that once oxygen evolution stopping, the pore growth must be stopped, and the pores must be sealed by the above compact oxide. A novel composite film of the anodic oxide is presented. All of the above conclusively show that in the forming process of PAA, an appropriate magnitude of electronic current ensures the oxygen evolution and the pores formation, an appropriate magnitude of ionic current ensures the oxide formation and growth of pore walls.
    • Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 61171043, 51077072), and the National Science and Technology Major Project of the Ministry of Science and Technology of China (Grant No. 2009ZX01021-002).
    [1]

    Platschek B, Keilbach A, Bein T 2011 Adv. Mater. 23 2395

    [2]

    Huang C, Jiang J, Lu M, Sun L, Meletis E I, Hao Y 2009 Nano Lett. 9 4297

    [3]

    Gu J J, Han J R, Cheng F W, Zhao G L, Liu L H, Sun H Y 2012 Acta Phys. Sin. 61 097503 (in Chinese) [顾建军, 韩金荣, 成福伟, 赵国良, 刘力虎, 孙会元 2012 61 097503]

    [4]

    Wang X L Q, Zhang D X, Zhang H J 2011 Acta Phys. Sin. 60 058104 (in Chinese) [王旭龙琦, 张冬仙, 章海军 2011 60 058104]

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    Li Q, Wang K G, Dang W J, Hui D, Ren Z Y, Bai J T 2010 Acta Phys. Sin. 59 5851(in Chinese) [李强, 王凯歌, 党维军, 惠丹, 任兆玉, 白晋涛 2010 59 5851]

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    Wu Z G, Zhang P J, Xu L, Li S K, Wang J, Li X D, Yan P X 2010 Acta Phys. Sin. 59 438 (in Chinese) [吴志国, 张鹏举, 徐亮, 李拴魁, 王君, 李旭东, 闫鹏勋 2010 59 438]

    [7]

    Wang C W, Ma B H, Li Y, Chen J B, Wang J, Liu W M 2008 Acta Phys. Sin. 57 5800 (in Chinese) [王成伟, 马保宏, 李燕, 陈建彪, 王建, 刘维民 2008 57 5800]

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    Lin J, Liu K, Chen X F 2011 Small 7 1784

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    Habazaki H, Teraoka M, Aoki Y, Skeldon P, Thompson G E 2010 Electrochim. Acta 55 3939

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    Lee K, Kim D, Roy P, Paramasivam I, Birajdar B I, Spiecker E, Schmuki P 2010 J. Am. Chem. Soc. 132 1478

    [11]

    Li S Q, Yin J B, Zhang G M 2010 Sci. China. Chem. 53 1068 (in Chinese) [李仕琦, 尹建波, 张耿民 2010 中国科学: 化学 53 1068]

    [12]

    Wang D A, Liu Y, Yu B, Zhou F, Liu W M 2009 Chem. Mater. 21 1198

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    Jessensky O, Müller F, Gösele U 1998 Appl. Phys. Lett. 72 1173

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    Li A P, Müller F, Birner A, Nielsch K, Gösele U 1998 J. Appl. Phys. 84 6023

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    Nielsch K, Choi J, Schwirn K, Wehrspohn R B, Gösele U 2002 Nano Lett. 2 677

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    Lee W, Schwirn K, Steinhart M, Pippel E, Scholz R, Gösele U 2008 Nat. Nanotechnol. 3 234

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    Skeldon P, Thompson G E, Garcia-Vergara S J, Iglesias-Rubianes L, Blanco-Pinzon C E 2006 Electrochem. Solid. St. 9 B47

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    Garcia-Vergara S J, Skeldon P, Thompson G E, Habazaki H 2006 Electrochim. Acta 52 681

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    Garcia-Vergara S J, Habazaki H, Skeldon P, Thompson G E 2010 Electrochim. Acta 55 3175

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    Houser J E, Hebert K R 2009 Nat. Mater. 8 415

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    Houser J E, Hebert K R 2006 J. Electrochem. Soc. 153 B566

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    Li D D, Zhao L, Jiang C H, Lu J G 2010 Nano Lett. 10 2766

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    Li D D, Jiang C H, Jiang J H, Lu J G 2009 Chem. Mater. 21 253

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    Su Z X, Zhou W Z 2008 Adv. Mater. 20 3663

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    Su Z X, Bühl M, Zhou W Z 2009 J. Am. Chem. Soc. 131 8697

    [26]

    Su Z X, Zhou W Z 2011 J. Mater. Chem. 21 357

    [27]

    Berger S, Hahn R, Roy P, Schmuki P 2010 Phys. Status Solidi B 247 2424

    [28]

    Roy P, Berger S, Schmuki P 2011 Angew. Chem. Int. Ed. 50 2904

    [29]

    Liu H W, Guo H M, Wang Y L, Shen C M, Yang H T, Wang Y T, Wei L 2004 Acta Phys. Sin. 53 656 (in Chinese) [刘虹雯,郭海明,王业亮,申承民,杨海涛,王雨田,魏龙 2004 53 656]

    [30]

    Zhu X F, Han H, Song Y, Duan W Q 2012Acta Phys. Chim. Sin. 28 1291 (in Chinese) [朱绪飞, 韩华, 宋晔, 段文强 2012 物理化学学报 28 1291]

    [31]

    Patermarakis G, Moussoutzanis K 2009 Electrochim. Acta 54 2434

    [32]

    Patermarakis G 2009 J. Electroanal. Chem. 635 39

    [33]

    Keller F, Hunter M S, Robinson D L 1953 J. Electrochem. Soc. 100 411

    [34]

    Diggle J W, Downie T C, Goulding C W 1969 Chem. Rev. 69 365

    [35]

    O'Sullivan J P, Wood G C 1970 Proc. R. Soc. Lond. A 317 511

    [36]

    Thompson G E, Furneaux R C, Wood G C, Richardson J A, Goode J S 1978 Nature 272 433

    [37]

    Thompson G E, Wood G C 1981 Nature 290 230

    [38]

    Furneaux R C, Rigby W R, Davidson A P 1989 Nature 337 147

    [39]

    Parkhutik V P, Shershulsky V I 1992 J. Phys. D: Appl. Phys. 25 1258

    [40]

    Thompson G E 1997 Thin Solid Films 297 192

    [41]

    Masuda H, Hasegwa F, Ono S 1997 J. Electrochem. Soc. 144 L127

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    Poinern G E J, Ali N, Fawcett D 2011 Materials 4 487

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    Su Z X, Zhou W Z 2011 J. Mater. Chem. 21 8955

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    Li Y, Shimada H, Sakairi M, Shigyo K, Takahashi H, Seo M 1997 J. Electrochem. Soc. 144 866

    [45]

    Zhu X F, Liu L, Zhao B C 2003 The Chinese Journal of Nonferrous Metals 13 1031 (in Chinese) [朱绪飞, 刘 霖, 赵宝昌 2003 中国有色金属学报 13 1031]

    [46]

    Macak J M, Tsuchiya H, Ghicov A, Yasuda K, Hahn R, Bauer S, Schmuki P 2007 Curr. Opi. Solid. St. M. 11 3

    [47]

    Ghicov A, Schmuki P 2009 Chem. Commun. 45 2791

    [48]

    Li F Y, Zhang L, Metzger R M 1998 Chem. Mater. 10 2470

    [49]

    Albella J M, Montero I, Martinez-Duart J M 1987 Electrochim. Acta 32 255

    [50]

    Zhu X F, Liu L, Song Y, Jia H, Yu H, Xiao X, Yang X 2008 Mater. Lett. 62 4038

    [51]

    Zhu X F, Liu L, Song Y, Jia H, Yu H, Xiao X, Yang X 2008 Monatsh. Chem. 139 999

    [52]

    Crossland A C, Habazaki H, Shimizu K, Skeldon P, Thompson G E, Wood G C, Zhou X, Smith C J 1999 Corros. Sci. 41 1945

    [53]

    Zhou X, Thompson G E, Habazaki H, Paez M A, Shimizu K, Skeldon P, Wood G C 2000 J. Electrochem. Soc. 147 1747

    [54]

    Habazaki H, Konno H, Shimizu K, Nagata S, Skeldon P, Thompson G E 2004 Corros. Sci. 46 2041

    [55]

    Schwirn K, Lee W, Hillebrand R, Steinhart M, Nielsch K, Gösele U 2008 ACS Nano 2 302

    [56]

    Lee W, Scholz R, Gösele U 2008 Nano Lett. 8 2155

    [57]

    Chung C K, Zhou R X, Liu T Y, Chang W T 2009 Nanotechnology 20 055301

    [58]

    Ispas A, Bund A, Vrublevsky I 2010 J. Solid State Electrochem. 14 2121

    [59]

    Li Y, Ling Z Y, Hu X, Liu Y S, Chang Y 2011 J. Mater. Chem. 21 9661

    [60]

    Li Y, Ling Z Y, Hu X, Liu Y S, Chang Y 2011 Chem. Commun. 47 2173

    [61]

    Zhang R, Jiang K M, Zhu Y, Qi H Y, Ding G Q 2011 Appl. Surf. Sci. 258 586

    [62]

    Patermarakis G, Moussoutzanis K 2011 J. Electroanal. Chem. 659 176

  • [1]

    Platschek B, Keilbach A, Bein T 2011 Adv. Mater. 23 2395

    [2]

    Huang C, Jiang J, Lu M, Sun L, Meletis E I, Hao Y 2009 Nano Lett. 9 4297

    [3]

    Gu J J, Han J R, Cheng F W, Zhao G L, Liu L H, Sun H Y 2012 Acta Phys. Sin. 61 097503 (in Chinese) [顾建军, 韩金荣, 成福伟, 赵国良, 刘力虎, 孙会元 2012 61 097503]

    [4]

    Wang X L Q, Zhang D X, Zhang H J 2011 Acta Phys. Sin. 60 058104 (in Chinese) [王旭龙琦, 张冬仙, 章海军 2011 60 058104]

    [5]

    Li Q, Wang K G, Dang W J, Hui D, Ren Z Y, Bai J T 2010 Acta Phys. Sin. 59 5851(in Chinese) [李强, 王凯歌, 党维军, 惠丹, 任兆玉, 白晋涛 2010 59 5851]

    [6]

    Wu Z G, Zhang P J, Xu L, Li S K, Wang J, Li X D, Yan P X 2010 Acta Phys. Sin. 59 438 (in Chinese) [吴志国, 张鹏举, 徐亮, 李拴魁, 王君, 李旭东, 闫鹏勋 2010 59 438]

    [7]

    Wang C W, Ma B H, Li Y, Chen J B, Wang J, Liu W M 2008 Acta Phys. Sin. 57 5800 (in Chinese) [王成伟, 马保宏, 李燕, 陈建彪, 王建, 刘维民 2008 57 5800]

    [8]

    Lin J, Liu K, Chen X F 2011 Small 7 1784

    [9]

    Habazaki H, Teraoka M, Aoki Y, Skeldon P, Thompson G E 2010 Electrochim. Acta 55 3939

    [10]

    Lee K, Kim D, Roy P, Paramasivam I, Birajdar B I, Spiecker E, Schmuki P 2010 J. Am. Chem. Soc. 132 1478

    [11]

    Li S Q, Yin J B, Zhang G M 2010 Sci. China. Chem. 53 1068 (in Chinese) [李仕琦, 尹建波, 张耿民 2010 中国科学: 化学 53 1068]

    [12]

    Wang D A, Liu Y, Yu B, Zhou F, Liu W M 2009 Chem. Mater. 21 1198

    [13]

    Jessensky O, Müller F, Gösele U 1998 Appl. Phys. Lett. 72 1173

    [14]

    Li A P, Müller F, Birner A, Nielsch K, Gösele U 1998 J. Appl. Phys. 84 6023

    [15]

    Nielsch K, Choi J, Schwirn K, Wehrspohn R B, Gösele U 2002 Nano Lett. 2 677

    [16]

    Lee W, Schwirn K, Steinhart M, Pippel E, Scholz R, Gösele U 2008 Nat. Nanotechnol. 3 234

    [17]

    Skeldon P, Thompson G E, Garcia-Vergara S J, Iglesias-Rubianes L, Blanco-Pinzon C E 2006 Electrochem. Solid. St. 9 B47

    [18]

    Garcia-Vergara S J, Skeldon P, Thompson G E, Habazaki H 2006 Electrochim. Acta 52 681

    [19]

    Garcia-Vergara S J, Habazaki H, Skeldon P, Thompson G E 2010 Electrochim. Acta 55 3175

    [20]

    Houser J E, Hebert K R 2009 Nat. Mater. 8 415

    [21]

    Houser J E, Hebert K R 2006 J. Electrochem. Soc. 153 B566

    [22]

    Li D D, Zhao L, Jiang C H, Lu J G 2010 Nano Lett. 10 2766

    [23]

    Li D D, Jiang C H, Jiang J H, Lu J G 2009 Chem. Mater. 21 253

    [24]

    Su Z X, Zhou W Z 2008 Adv. Mater. 20 3663

    [25]

    Su Z X, Bühl M, Zhou W Z 2009 J. Am. Chem. Soc. 131 8697

    [26]

    Su Z X, Zhou W Z 2011 J. Mater. Chem. 21 357

    [27]

    Berger S, Hahn R, Roy P, Schmuki P 2010 Phys. Status Solidi B 247 2424

    [28]

    Roy P, Berger S, Schmuki P 2011 Angew. Chem. Int. Ed. 50 2904

    [29]

    Liu H W, Guo H M, Wang Y L, Shen C M, Yang H T, Wang Y T, Wei L 2004 Acta Phys. Sin. 53 656 (in Chinese) [刘虹雯,郭海明,王业亮,申承民,杨海涛,王雨田,魏龙 2004 53 656]

    [30]

    Zhu X F, Han H, Song Y, Duan W Q 2012Acta Phys. Chim. Sin. 28 1291 (in Chinese) [朱绪飞, 韩华, 宋晔, 段文强 2012 物理化学学报 28 1291]

    [31]

    Patermarakis G, Moussoutzanis K 2009 Electrochim. Acta 54 2434

    [32]

    Patermarakis G 2009 J. Electroanal. Chem. 635 39

    [33]

    Keller F, Hunter M S, Robinson D L 1953 J. Electrochem. Soc. 100 411

    [34]

    Diggle J W, Downie T C, Goulding C W 1969 Chem. Rev. 69 365

    [35]

    O'Sullivan J P, Wood G C 1970 Proc. R. Soc. Lond. A 317 511

    [36]

    Thompson G E, Furneaux R C, Wood G C, Richardson J A, Goode J S 1978 Nature 272 433

    [37]

    Thompson G E, Wood G C 1981 Nature 290 230

    [38]

    Furneaux R C, Rigby W R, Davidson A P 1989 Nature 337 147

    [39]

    Parkhutik V P, Shershulsky V I 1992 J. Phys. D: Appl. Phys. 25 1258

    [40]

    Thompson G E 1997 Thin Solid Films 297 192

    [41]

    Masuda H, Hasegwa F, Ono S 1997 J. Electrochem. Soc. 144 L127

    [42]

    Poinern G E J, Ali N, Fawcett D 2011 Materials 4 487

    [43]

    Su Z X, Zhou W Z 2011 J. Mater. Chem. 21 8955

    [44]

    Li Y, Shimada H, Sakairi M, Shigyo K, Takahashi H, Seo M 1997 J. Electrochem. Soc. 144 866

    [45]

    Zhu X F, Liu L, Zhao B C 2003 The Chinese Journal of Nonferrous Metals 13 1031 (in Chinese) [朱绪飞, 刘 霖, 赵宝昌 2003 中国有色金属学报 13 1031]

    [46]

    Macak J M, Tsuchiya H, Ghicov A, Yasuda K, Hahn R, Bauer S, Schmuki P 2007 Curr. Opi. Solid. St. M. 11 3

    [47]

    Ghicov A, Schmuki P 2009 Chem. Commun. 45 2791

    [48]

    Li F Y, Zhang L, Metzger R M 1998 Chem. Mater. 10 2470

    [49]

    Albella J M, Montero I, Martinez-Duart J M 1987 Electrochim. Acta 32 255

    [50]

    Zhu X F, Liu L, Song Y, Jia H, Yu H, Xiao X, Yang X 2008 Mater. Lett. 62 4038

    [51]

    Zhu X F, Liu L, Song Y, Jia H, Yu H, Xiao X, Yang X 2008 Monatsh. Chem. 139 999

    [52]

    Crossland A C, Habazaki H, Shimizu K, Skeldon P, Thompson G E, Wood G C, Zhou X, Smith C J 1999 Corros. Sci. 41 1945

    [53]

    Zhou X, Thompson G E, Habazaki H, Paez M A, Shimizu K, Skeldon P, Wood G C 2000 J. Electrochem. Soc. 147 1747

    [54]

    Habazaki H, Konno H, Shimizu K, Nagata S, Skeldon P, Thompson G E 2004 Corros. Sci. 46 2041

    [55]

    Schwirn K, Lee W, Hillebrand R, Steinhart M, Nielsch K, Gösele U 2008 ACS Nano 2 302

    [56]

    Lee W, Scholz R, Gösele U 2008 Nano Lett. 8 2155

    [57]

    Chung C K, Zhou R X, Liu T Y, Chang W T 2009 Nanotechnology 20 055301

    [58]

    Ispas A, Bund A, Vrublevsky I 2010 J. Solid State Electrochem. 14 2121

    [59]

    Li Y, Ling Z Y, Hu X, Liu Y S, Chang Y 2011 J. Mater. Chem. 21 9661

    [60]

    Li Y, Ling Z Y, Hu X, Liu Y S, Chang Y 2011 Chem. Commun. 47 2173

    [61]

    Zhang R, Jiang K M, Zhu Y, Qi H Y, Ding G Q 2011 Appl. Surf. Sci. 258 586

    [62]

    Patermarakis G, Moussoutzanis K 2011 J. Electroanal. Chem. 659 176

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Publishing process
  • Received Date:  20 May 2012
  • Accepted Date:  13 September 2012
  • Published Online:  05 November 2012

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