Abstract
Heat treatment of Zr-24 at% Ti alloy with barrier-type dielectric anodic oxide films was conducted at 473 K in air to examine the thermal stability of the dielectric oxide films for possible electrolytic capacitor application. The anodic oxide film was formed by anodizing of the alloy at 50 V for 30 min in 0.1 mol dm−3 ammonium pentaborate electrolyte. The anodic oxide film of 125 nm thickness was crystalline, containing both monoclinic and tetragonal ZrO2 phase. It was found that marked thickening of the oxide film with generation of cracks occurred during heat treatment at 473 K. Thus, the dielectric loss was largely increased along with the capacitance increase. In contrast, the anodic oxide film formed on the oxygen-incorporated alloy remained uniform, and no significant increase in dielectric loss was observed even after the heat treatment. The capacitance of the anodic film became as high as 4.8 mF m−2, which was nearly twice that on Ta. The high capacitance was associated with the preferential formation of tetragonal ZrO2 phase in the anodic oxide film on the oxygen-incorporated alloy. Findings indicated that the oxygen-incorporated Zr-Ti alloy is a promising novel material for capacitor application.
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References
Gray JE, Luan B (2002) Protective coatings on magnesium and its alloys—a critical review. J Alloys Compd 336:88–113
Thompson GE, Skeldon P, Zhou X, Shimizu K, Habazaki H, Smith CFE (2003) Improving the performance of aerospace alloys. Aircr Eng Aerosp Tec 75(4):372–379
Blawert C, Dietzel W, Ghali E, Song GL (2006) Anodizing treatments for magnesium alloys and their effecton corrosion resistance in various environments. Adv Eng Mater 8(6):511–533
Watanabe K, Sakairi M, Takahashi H, Hirai S, Yamaguchi S (1999) Formation of Al-Zr composite oxide films on aluminum by sol-gel coating and anodizing. J Electroanal Chem 473(1–2):250–255
Lu Q, Mato S, Skeldon P, Thompson GE, Masheder D, Habazaki H, Shimizu K (2002) Anodic film growth on tantalum in dilute phosphoric acid solution at 20 and 85°C. Electrochim Acta 47(17):2761–2767
Pozdeev-Freeman Y, Gladkikh A (2001) Effect of thermal oxide on the crystallization of the anodic Ta2O5 film. J Electron Mater 30(8):931–936
Freeman Y, Alapatt GF, Harrell WR, Lessner P (2012) Electrical characterization of high voltage polymer tantalum capacitors. J Electrochem Soc 159(10):A1646–A1651
Freeman Y, Alapatt GF, Harrell WR, Luzinov I, Lessner P, Qazi J (2013) Anomalous currents in low voltage polymer tantalum capacitors. ECS J Solid State Sci Technol 2(11):N197–N204
Roy P, Berger S, Schmuki P (2011) TiO2 nanotubes: synthesis and applications. Angew Chem Int Ed 50(13):2904–2939
Kowalski D, Kim D, Schmuki P (2013) TiO2 nanotubes, nanochannels and mesosponge: self-organized formation and applications. Nano Today 8(3):235–264
Lee W, Park SJ (2014) Porous anodic aluminum oxide: anodization and templated synthesis of functional nanostructures. Chem Rev 114(15):7487–7556
Habazaki H, Ogasawara T, Fushimi K, Shimizu K, Nagata S, Izumi T, Skeldon P, Thompson GE (2008) Inhibition of field crystallization of anodic niobium oxide by incorporation of silicon species. Electrochim Acta 53(28):8203–8210
Habazaki H, Ogasawara T, Konno H, Shimizu K, Nagata S, Skeldon P, Thompson GE (2007) Field crystallization of anodic niobia. Corros Sci 49(2):580–593
Habazaki H, Ogasawara T, Konno H, Shimizu K, Nagata S, Asami K, Takayama K, Skeldon P, Thompson GE (2006) Suppression of field crystallization of anodic niobia by oxygen. J Electrochem Soc 153(5):B173–B177
Habazaki H, Ogasawara T, Konno H, Shimizu K, Asami K, Nagata S, Takayama K, Skeldon P, Thompson GE (2006) Field crystallization of anodic niobia on Nb-O substrates. ECS Trans 1(4):343–349
Nagahara K, Sakairi M, Takahashi H, Nagata S, Matsumoto K, Takayama K, Oda Y (2004) Influence of current density on the structure and dielectric properties of anodic oxide films on niobium. J Surf Finish Soc Jpn 55(12):943–951
Nagahara K, Sakairi M, Takahashi H, Matsumoto K, Takayama K, Oda Y (2004) Change in the structure and dielectric properties of niobium anodic oxide films during potentiostatic anodizing. Elechemistry 72(9):624–632
Lakhiani DM, Shreir LL (1960) Crystallization of amorphous Nb oxide during anodic oxidation. Nature 188:49–50
Modestov AD, Davydov AD (1999) Capacitance and photocurrent study of electronic properties of anodic oxide films on Nb and Ta. Evaluation of the ionized donor concentration profile in Nb2O5 film. J Electroanal Chem 460:214–225
Habazaki H, Ogasawara T, Konno H, Shimizu K, Asami K, Saito K, Nagata S, Skeldon P, Thompson GE (2005) Growth of anodic oxide films on oxygen-containing niobium. Electrochim Acta 50(27):5334–5339
Habazaki H, Matsuo T, Konno H, Shimizu K, Nagata S, Takayama K, Oda Y, Skeldon P, Thompson GE (2003) Formation of N2O gas bubbles in anodic films on NbNx alloys. Thin Solid Films 429(1–2):159–166
Habazaki H, Matsuo T, Konno H, Shimizu K, Nagata S, Matsumoto K, Takayama K, Oda Y, Skeldon P, Thompson GE (2003) Influence of silicon species on the electric properties of anodic niobia. Electrochim Acta 48(23):3519–3526
Habazaki H, Matsuo T, Konno H, Shimizu K, Matsumoto K, Takayama K, Oda Y, Skeldon P, Thompson GE (2003) Analysis of anodic films on Nb and NbNx by glow discharge optical emission spectroscopy. Surf Interface Anal 35(7):618–622
Aladjem A (1973) Anodic oxidation of titanium and its alloys. J Mater Sci 8:688–704
Dyer CK, Leach JSL (1978) Breakdown and efficiency of anodic oxide growth on titanium. J Electrochem Soc 125:1032–1038
Habazaki H, Uozumi M, Konno H, Shimizu K, Skeldon P, Thompson GE (2003) Crystallization of anodic titania on titanium and its alloys. Corros Sci 45(9):2063–2073
Habazaki H, Uozumi M, Konno H, Nagata S, Shimizu K (2003) Formation of barrier-type amorphous anodic films on Ti-Mo alloys. Surf Coat Technol 169:151–154
Habazaki H, Uozumi M, Konno H, Shimizu K, Nagata S, Asami K, Matsumoto K, Takayama K, Oda Y, Skeldon P, Thompson GE (2003) Influences of structure and composition on growth of anodic oxide films on Ti-Zr alloys. Electrochim Acta 48(20–22):3257–3266
Habazaki H, Uozumi M, Konno H, Shimizu K, Nagata S, Takayama K, Oda Y, Skeldon P, Thompson GE (2005) Influence of film composition on the structure and dielectric properties of anodic films on Ti-W alloys. J Electrochem Soc 152(8):B263–B270
Tanvir MT, Fushimi K, Shimizu K, Nagata S, Skeldon P, Thompson GE, Habazaki H (2007) Influence of silicon on the growth of barrier-type anodic films on titanium. Electrochim Acta 52(24):6834–6840
Di Franco F, Santamaria M, Di Quarto F, Macaluso R, Mosca M, Cali C (2014) Electrochemical fabrication and physicochemical characterization of metal/high-k insulating oxide/polymer/electrolyte junctions. J Phys Chem C 118(51):29973–29980
Di Franco F, Bocchetta P, Cali C, Mosca M, Santamaria M, Di Quarto F (2011) Electrochemical fabrication of metal/oxide/conducting polymer junction. J Electrochem Soc 158(1):H50–H54
Habazaki H, Shimizu K, Nagata S, Asami K, Takayama K, Oda Y, Skeldon P, Thompson GE (2005) Inter-relationship between structure and dielectric properties of crystalline anodic zirconia. Thin Solid Films 479(1–2):144–151
Santamaria M, Di Quarto F, Habazaki H (2008) Influences of structure and composition on the photoelectrochemical behaviour of anodic films on Zr and Zr-20 at.% Ti. Electrochim Acta 53(5):2272–2280
Climent-Font A, Watjen V, Bax H (1992) Quantitative RBS analysis using RUMP. On the accuracy of the He stopping in Si. Nucle Instr and Meth B71:81–86
Habazaki H, Koyama S, Aoki Y, Sakaguchi N, Nagata S (2011) Enhanced capacitance of composite anodic ZrO2 films comprising high permittivity oxide nanocrystals and highly resistive amorphous oxide matrix. ACS App Mater Interfaces 3(7):2665–2670
Koyama S, Aoki Y, Sakaguchi N, Nagata S, Habazaki H (2010) Phase transformation and capacitance enhancement of anodic ZrO2-SiO2. J Electrochem Soc 157(12):C444–C451
Brossmann U, Wurschum R, Sodervall U, Schaefer HE (1999) Oxygen diffusion in ultrafine grained monoclinic ZrO2. J Appl Phys 85(11):7646–7654
Pringle JPS (1980) The anodic oxidation of superimposed metallic layers: theory. Electrochim Acta 25:1423–1437
Koyama S, Aoki Y, Nagata S, Habazaki H (2011) Formation and dielectric properties of anodic oxide films on Zr-Al alloys. J Solid State Electrochem 15:2221–2229
Koyama S, Aoki Y, Nagata S, Kimura H, Habazaki H (2010) Amorphous-to-crystalline transition of silicon-incorporated anodic ZrO2 and improved dielectric properties. Electrochim Acta 55(9):3144–3151
San Andres E, Toledano-Luque M, del Prado A, Navacerrada MA, Martil I, Gonzalez-Diaz G, Bohne W, Rohrich J, Strub E (2005) Physical properties of high pressure reactively sputtered TiO2. J Vacuum Sci Technol A 23(6):1523–1530
Thompson DP, Dickins AM, Thorp JS (1992) The dielectric-properties of zirconia. J Mater Sci 27(8):2267–2271
Pozdeev-Freeman Y, Gladkikh A, Karpovski M, Palevski A (1998) Effect of dissolved oxygen on thermal oxidation in Ta2O5/Ta sandwiches. J Electron Mater 27:1034–1037
Pozdeev-Freeman Y, Rozenberg Y, Gladkikh A, Karpovski M, Palevski A (1998) Critical oxygen content in porous anodes of solid tantalum capacitors. J Mater Sci Mater Electron 9(4):309–311
Vermilyea DA (1955) The crystallization of anodic tantalum oxide films in the presence of a strong electric field. J Electrochem Soc 102:207–214
Nagahara K, Sakairi M, Takahashi H, Matsumoto K, Takayama K, Oda Y (2007) Mechanism of formation and growth of sunflower-shaped imperfections in anodic oxide films on niobium. Electrochim Acta 52(5):2134–2145
Su X, Viste M, Hossick-Schott J, Yang L, Sheldon BW (2015) Reassessment of degradation mechanisms in anodic tantalum oxide capacitors under high electric fields. J Mater Sci 50(2):960–969
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The present study was supported in part by Nanotechnology Platform Program of the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan.
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Habazaki, H., Kobayashi, K., Tsuji, E. et al. Highly increased capacitance and thermal stability of anodic oxide films on oxygen-incorporated Zr-Ti alloy. J Solid State Electrochem 21, 2807–2816 (2017). https://doi.org/10.1007/s10008-017-3607-2
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DOI: https://doi.org/10.1007/s10008-017-3607-2