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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 林招松(Chao-Sung Lin) | |
dc.contributor.author | Chia-Hsuan Wang | en |
dc.contributor.author | 王家宣 | zh_TW |
dc.date.accessioned | 2021-06-15T16:16:11Z | - |
dc.date.available | 2023-08-31 | |
dc.date.copyright | 2020-08-24 | |
dc.date.issued | 2020 | |
dc.date.submitted | 2020-08-14 | |
dc.identifier.citation | [1] Youssef, K.M., et al, A Novel Low-Density, High Hardness, High-entropy Alloy with Close-packed Single-phase Nanocrystalline Structures. Materials Research Letters, 2015. 3(2):p. 95-99 [2] I.J. Polmear, Light Alloys Metallurgy of the Light Metals. Third ed., London: Arnold, 1995. [3] J.E. Hath, Aluminum: properties and physical metallurgy. American Society for Metals, Metals Park, Ohio, 1984. [4] 黃振賢. 機械材料. 修訂二版: 新文京開發, 2003. [5] G. Sha, K.A.Q. O’Reilly, B. Cantor, J. Worth, R. Hamerton, R. Hamerton, Growth related metastable phase selection in a 6xxx series wrought Al alloy. Mater. Sci. Eng. A 304-306 (2001) 612-616. [6] G. Sha, K.A.Q. O’Reilly, B. Cantor, J.M. Titchmarsh, R.G. Hamerton, Quasi-peritectic solidification reactions in 6xxx series wrought Al alloys. Acta Mater. 51 (2003) 1883-1897. [7] L Bäckerud, L., et al. Solidification Characteristics of Aluminum Alloys: Wrought alloys. Skanaluminum,1986. [8] A.L. Dons, The Alstruc homogenization model for industrial aluminum alloys. J. Light Met. 1 (2001) 133-149. [9] S.N. Samaras and G.N. Haidemenopoulos, Modelling of microsegregation and homogenization of 6061 extrudable Al-alloy. Journal of Materials Processing Technology,2007. 194(1):63-73. [10] Totten, G.E. and D.S. MacKenzie (2003). Handbook of Aluminum: Volume 2:Alloy Production and Materials Manufacturing, CRC Press [11] Dutta, I., S.M. Allen, and J.L. Hafley, Effect of reinforcement on the aging response of cast 6061 Al-Al2O3 particulate composites. Metallurgical Transactions a-Physical Metallurgy and Materials Science, 1991. 22(11): p. 2553-2563. [12] Murayama, M. and K. Hono, Pre-precipitate clusters and precipitation processes in Al-Mg-Si alloys. Acta Materialia, 1999. 47(5): p. 1537-1548. [13] Jacobs, M. H., Phil. Mag., 1972, 26, 1. [14] Pourbaix, M. and J. Franklin (1966). Atlas of Electrochemical Equilibria in Aqueous Solution, Elsevier Science Technology. [15] Adhikari, S. and K.R. Hebert, Factors controlling the time evolution of the corrosion potential of aluminum in alkaline solutions. Corrosion Science, 2008. 50(5): p. 1414-1421. [16] E. McCafferty, Introduction to Corrosion Science. New Work: Springer, 2010. [17] Andreatta, F., H. Terryn, and J.H.W. de Wit, Effect of solution heat treatment on galvanic coupling between intermetallics and matrix in AA7075-T6. Corrosion Science, 2003. 45(8): p. 1733-1746. [18] Zhu, Y., K. Sun, and G.S. Frankel, Intermetallic Phases in Aluminum Alloys and Their Roles in Localized Corrosion. Journal of The Electrochemical Society, 2018. 165(11): p. C807-C820. [19] Zeng, F.L., et al., Corrosion mechanism associated with Mg2Si and Si particles in Al-Mg-Si alloys. Transactions of Nonferrous Metals Society of China, 2011. 21(12): p. 2559-2567. [20] Juttner, K., ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY (EIS) OF CORROSION PROCESSES ON INHOMOGENEOUS SURFACES. Electrochimica Acta, 1990. 35(10): p. 1501-1508. [21] Mansfeld, F., ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY (EIS) AS A NEW TOOL FOR INVESTIGATING METHODS OF CORROSION PROTECTION. Electrochimica Acta, 1990. 35(10): p. 1533-1544. [22] Mansfeld, F., et al., PITTING AND PASSIVATION OF AL-ALLOYS AND AL-BASED METAL MATRIX COMPOSITES. Journal of the Electrochemical Society, 1990. 137(1): p. 78-82. [23] Fabian, R. (1993). Vacuum Technology: Practical Heat Treating and Brazing, ASM International. [24] Shi, H., et al., Effect of alkaline etching on microstructure and anticorrosion performance of anodic film on Al-Mg-Si alloy. Corrosion Science, 2020. 169. [25] P.L. Hagans and C. Haas, Chromate conversion coatings, ASM handbook, 5, 405-411 (1994) [26] Kendig, M., et al., Role of hexavalent chromium in the inhibition of corrosion of aluminum alloys. Surface Coatings Technology, 2001. 140(1): p. 58-66. [27] Munson, C.A., S.A. McFall-Boegeman, and G.M. Swain, Cross comparison of TCP conversion coating performance on aluminum alloys during neutral salt-spray and thin-layer mist accelerated degradation testing. Electrochimica Acta, 2018. 282: p. 171-184. [28] Qi, J.T., et al., Trivalent chromium conversion coating formation on aluminium. Surface Coatings Technology, 2015. 280: p. 317-329. [29] Qi, J., et al., Formation of a Trivalent Chromium Conversion Coating on AA2024-T351 Alloy. Journal of the Electrochemical Society, 2016. 163(2): p. C25-C35. [30] Li, L.L., D.Y. Kim, and G.M. Swain, Transient Formation of Chromate in Trivalent Chromium Process (TCP) Coatings on AA2024 as Probed by Raman Spectroscopy. Journal of the Electrochemical Society, 2012. 159(8): p. C326-C333. [31] Li, L.L., et al., The Formation, Structure, Electrochemical Properties and Stability of Trivalent Chrome Process (TCP) Coatings on AA2024. Journal of the Electrochemical Society, 2011. 158(9): p. C274-C283. [32] Li, L.L., K.P. Doran, and G.M. Swain, Electrochemical Characterization of Trivalent Chromium Process (TCP) Coatings on Aluminum Alloys 6061 and 7075. Journal of the Electrochemical Society, 2013. 160(8): p. C396-C401. [33] T.R. Giles, D.R. Vonk, and S.-L. Favero, in, p. 172, Henkel Corporation, Sao Paulo, Brazil (2012) [34] T.R. Giles, B.H. Goodreau, W.E. Fristad, J. Kroemer, and M. Frank, SAE Int. J. Mater. Manuf., 1, 575(2008). [35] Milošev, I. and G. Frankel, Conversion Coatings Based on Zirconium and/or Titanium. Journal of The Electrochemical Society, 2018. 165(3): p. C127. [36] Nordlien, J.H., et al., Formation of a zirconium-titanium based conversion layer on AA 6060 aluminium. Surface Coatings Technology, 2002. 153(1): p. 72-78. [37] Adhikari, S., et al., Hexafluorozirconic acid based surface pretreatments: Characterization and performance assessment. Electrochimica Acta, 2011. 56(4): p. 1912-1924. [38] Cerezo, J., et al., Initiation and growth of modified Zr-based conversion coatings on multi-metal surfaces. Surface Coatings Technology, 2013. 236: p. 284-289. [39] Cerezo, J., et al., Influence of surface hydroxyls on the formation of Zr-based conversion coatings on AA6014 aluminum alloy. Surface Coatings Technology, 2014. 254: p. 277-283. [40] Cerezo, J., et al., The effect of surface pre-conditioning treatments on the local composition of Zr-based conversion coatings formed on aluminium alloys. Applied Surface Science, 2016. 366: p. 339-347. [41] Sarfraz, A., et al., Role of Intermetallics and Copper in the Deposition of ZrO2 Conversion Coatings on AA6014. Journal of the Electrochemical Society, 2014. 161(12): p. C509-C516. [42] Cerezo, J., et al., The effect of conversion bath convection on the formation of Zr-based thin-film coatings on multi-metal surfaces. Materials and Corrosion-Werkstoffe Und Korrosion, 2016. 67(4): p. 361-367. [43] Li, L.L., A.L. Desouza, and G.M. Swain, In situ pH measurement during the formation of conversion coatings on an aluminum alloy (AA2024). Analyst, 2013. 138(15): p. 4398-4402. [44] Li, L.L., B.W. Whitman, and G.M. Swain, Characterization and Performance of a Zr/Ti Pretreatment Conversion Coating on AA2024-T3. Journal of the Electrochemical Society, 2015. 162(6): p. C279-C284. [45] Peng, D.D., et al., The formation and corrosion behavior of a zirconium-based conversion coating on the aluminum alloy AA6061. Journal of Coatings Technology and Research, 2016. 13(5): p. 837-850. [46] Brady, M.P., et al., Advanced characterization study of commercial conversion and electrocoating structures on magnesium alloys AZ31B and ZE10A. Surface Coatings Technology, 2016. 294: p. 164-176. [47] Lunder, O., et al., Formation and characterisation of Ti-Zr based conversion layers on AA6060 aluminium. Surface Coatings Technology, 2004. 184(2-3): p. 278-290. [48] Lunder, O., et al., Effect of pre-treatment on the durability of epoxy-bonded AA6060 aluminium joints. International Journal of Adhesion and Adhesives, 2004. 24(2): p. 107-117. [49] Li, L.L., et al., Structure and Corrosion Performance of a Non-Chromium Process (NCP) Zr/Zn Pretreatment Conversion Coating on Aluminum Alloys. Journal of the Electrochemical Society, 2016. 163(13): p. C718-C728. [50] Brown, Paul L. et al. Chemical Thermodynamics of Zirconium, 2015. [51] UNITED STATES OF AMERICA AS REPRESENTED (2018), U.S. Patent No. US9970115 B2 [52] Adhikari, S., et al., Hexafluorozirconic acid based surface pretreatments: Characterization and performance assessment. Electrochimica Acta, 2011. 56(4): p. 1912-1924. [53] Standard, A.S. T. M. B117-16, Standard Practice for Operating Salt Spray (Fog) Apparatus, ASTM International, West Conshohocken (2016) [54] Klingshirn, Claus F. et al. Zinc Oxide From Fundamental Properties Towards Novel Applications. 2010. [55] Callister, William D., and David G. Rethwisch. Materials Science and Engineering, 9th edition, SI version. Hoboken, NJ: Wiley, 2015. [56] Wikimedia Commons contributors, 'File:Wurtzite polyhedra.png,' Wikimedia Commons, the free media repository, <https://commons.wikimedia.org/w/index.php?title=File:Wurtzite_polyhedra.png oldid=161320121> [57] Cosslett, V. E., Practical Electron Microscopy. New York: Academic press Inc. Publishers, 1951. [58] Peter M. A. Sherwood, Introduction to Studies of Aluminum and its Compounds by XPS. Surface Science Spectra 5, 1 (1998). [59] Cerezo, J., et al., Influence of surface hydroxyls on the formation of Zr-based conversion coatings on AA6014 aluminum alloy. Surface Coatings Technology, 2014. 254: p. 277-283. [60] Våland, T. and G. Nilsson, The influence of F− ions on the electrochemical reactions on oxide-covered A1. Corrosion Science, 1977. 17(6): p. 449-459. [61] Pulfer, K., P.W. Schindler, and J.C. WestallRolf Grauer, Kinetics and mechanism of dissolution of bayerite (γ-Al(OH)3) in HNO3-HF solutions at 298.2°K. Journal of Colloid and Interface Science, 1984. 101(2): p. 554-564. [62] Farrah, H, J Slavek, and WF Pickering. Fluoride Interactions with Hydrous Aluminum Oxides and Alumina. Soil research. 25.1 (1987): 55–69. | |
dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/52487 | - |
dc.description.abstract | 鋁合金具有低密度、高比強度的優點,因此為現在主要的輕量化材料,雖然鋁合金的原生氧化層即具有抗蝕能力,但是在實際應用上,仍需要化成處理提升抗蝕性及塗裝性,由於傳統六價鉻的致癌性,目前許多研究以鋯化合物化成(以下稱鋯化成)取代。 本研究在探討6061鋁合金在鹼洗酸洗前處理及鋯化成處理後的膜層性質, 其中鋯化成主要分為三個部分做討論:一、測試Chemetall公司的Gardobond X4707商用藥水,並參考X4707藥水的ICP-OES元素檢測結果,以六氟鋯酸配置出模擬X4707的化成液組成,簡稱為FZA化成系統;為了更進一步提升鋯成膜速率和抗蝕特性,在後續討論以下主題,二、添加陽離子對FZA化成特性的影響,以及三、添加自由氟離子對FZA化成特性的影響。 6061鋁合金在經過鹼洗酸洗後,TEM橫截面影像顯示表面會披覆僅7至8 nm的氧化層,且均勻覆蓋在鋁基材和晶界上,該層主要由氧化鋁和氫氧化鋁組成,經過鹼洗脫脂和酸洗活化表面的試片才能接續進行鋯化成處理,EIS結果顯示自配FZA化成系統可以與X4707匹配,在鹽霧試驗結果中,鹼洗酸洗試片在七天測試即有嚴重脫色現象,FZA化成膜在鹽霧環境十四天後仍保有金屬光澤,由於10至15 nm厚的FZA膜層主要由氧化鋁、氫氧化鋁、氟化鋯、二氧化鋯組成,可見鋯物種併入確實有助於提升抗蝕性。 後續選擇以添加銅離子和鋅離子於FZA化成系統,期望藉此提升成膜速率以符合工業需求,然而銅離子會直接還原成銅顆粒遍布於鋁基材,伽凡尼效應與銅上較高的析氫速率都會加速鋁在腐蝕測試液中的溶解,鋅離子則會以鋅和氫氧化鋅的混合沉積於惰性一次析出物α-AlFeSi上,由於鋅的溶解度高,因此無法有效抑制鋁鐵矽相中鋁的溶解。歸納上述結果,可以知道添加陽離子並無助於提升FZA皮膜的抗蝕性,因此最後改為以添加自由氟離子做測試。 在添加氟離子於FZA化成系統的實驗中,50 ppm氟的添加後能使皮膜阻抗較FZA皮膜提升,且皮膜大概能增厚至15至20 nm,氟化鋯的沉積比例也會較FZA高,藉由氟的添加,能更有效率移除鋁的氧化層,進而更加驅動鋯成膜反應 使膜層更厚且均勻,然而實驗中也顯示氟的過量添加反而會抑制鋯沉積反應進行,使抗蝕性下降。 | zh_TW |
dc.description.abstract | In light of low density and high strength/weight ratio, aluminum alloys are the main lightweight materials. Although the native oxide layer on aluminum alloys is corrosion resistant, a conversion coating layer is still essential to enhance the corrosion resistance and adhesion of subsequent organic paintings in practical applications. However, as traditional hexavalent chromium conversion coatings (CCCs) are toxic and carcinogenic, many studies have found zirconium conversion coating as alternatives to CCCs. This research aims at understanding the properties of 6061 aluminum alloys (AA6061) after pretreatment and zirconium conversion coatings. Firstly, the properties of Gardobond X4707 commercial coating solution was investigated. Additionally, a hexafluorozirconic acid coating system, which was denoted as “FZA” , was designed based on the ICP-OES analysis data of X4707. Secondly, the effect of cation (e.g. Cu2+ and Zn2+) in the FZA was explored. Thirdly, the effect of fluoride ion in the FZA was investigated. The latter two parts focused on enhancing the coating formation rate and corrosion resistance. The TEM cross-sectional images show that a 7-8 nm Al2O3 and Al(OH)3 oxide layer is uniformly covered on the AA6061 substrate and grain boundary after pretreatment. The zirconium conversion coating treatment can be conducted after alkaline degreasing and acid deoxidation pretreatments. The EIS results reveal that the corrosion resistance of the FZA coating is comparable to that of X4707. In the salt spray test, black corrosion products were seen on most of the pretreatment specimen after 7-day exposure. However, the FZA-coated specimen can remain undamaged after 14-day exposure. From the results of TEM EDX mapping and XPS analysis, the FZA coating is about 10-15 thick, with the composition of Al2O3, Al(OH)3, ZrO2 and ZrF4. Thus it can be inferred that zirconium species deposited in the aluminum oxide can indeed improve the corrosion resistance of AA6061. In the next part, Cu2+ or Zn2+ was added in the FZA for enhancing the coating formation rate. However,the results show that Cu particles spread all over the AA6061 surface, resulting in the serious galvanic corrosion effect. Moreover, there is higher hydrogen exchange current density on Cu particles. Both result in accelerating the dissolution of AA6061 matrix. The Zn2+ addition, leads to the deposition of Zn and Zn(OH)2 mainly on noble constituent particles, α-AlFeSi. Due to the high solubility of zinc, it cannot effectively inhibit corrosion attacking on the AA6061 matrix from α-AlFeSi. As a result, the addition of Cu2+ or Zn2+ cannot improve the corrosion resistance of FZA coatings. The last part of this research is about the effect of the presence of fluoride ion in FZA. The EIS results show that 50 ppm fluoride ion addition can effectively increase the polarization resistance of FZA coating, which was denoted as “50 ppm F”. Moreover, the 50-ppm-F coating can be thickened to 15-20 nm. From the XPS results, the deposition proportion of ZrF4 is increased compared to the FZA coating. By adding fluoride ion, the aluminum oxide layer can be removed more efficiently. Therefore, the zirconium species deposition is more comprehensive, resulting in a more uniform and thicker coating film. However, the excessive addition of fluoride ion (> 100 ppm) inhibits the zirconium deposition reaction, which in turn decreases the corrosion resistance of FZA coating. | en |
dc.description.provenance | Made available in DSpace on 2021-06-15T16:16:11Z (GMT). No. of bitstreams: 1 U0001-0608202017154100.pdf: 7339988 bytes, checksum: 8818c423dcbcfeb6cad5c1a63a539251 (MD5) Previous issue date: 2020 | en |
dc.description.tableofcontents | 1 中文摘要 i 2 Abstract iii 3 總目錄 vi 4 圖目錄 ix 5 表目錄 xiii 1 第一章 前言 1 2 第二章 文獻回顧 2 2.1 鋁合金簡介 2 2.1.1 性質 2 2.1.2 種類及命名 3 2.2 熱處理型鋁合金析出物種類 4 2.2.1 一次析出物 4 2.2.2 分散相 6 2.2.3 析出強化相 8 2.3 鋁合金腐蝕 10 2.3.1 概述 10 2.3.2 孔蝕機制 12 2.4 前處理 17 2.4.1 鹼洗 17 2.4.2 酸洗 19 2.5 化成處理 20 2.5.1 六價鉻 20 2.5.2 三價鉻 22 2.5.3 鋯/鈦酸鹽 25 3 第三章 實驗步驟與方法 39 3.1 試片處理 39 3.2 化學組成分析 41 3.2.1 電感耦合電漿體光學發射光譜法 41 3.2.2 能量散佈光譜儀 41 3.2.3 X射線光電子能譜 42 3.3 微結構分析 42 3.3.1 掃描式電子顯微鏡 42 3.3.2 聚焦離子束與電子束顯微系統 43 3.3.3 穿透式電子顯微鏡 43 3.4 抗蝕性分析 44 3.4.1 開路電位 44 3.4.2 動電位極化曲線 45 3.4.3 電化學交流阻抗 46 3.4.4 鹽霧試驗 46 4 第四章 實驗結果與討論 47 4.1 鹼洗酸洗後對試片的影響 47 4.1.1 表面形貌與橫截面影像觀察 47 4.1.2 電化學交流阻抗 49 4.1.3 動電位極化曲線 52 4.2 不同鋯/鈦化成液之分析 54 4.2.1 Gardobond X4707化成液測試 54 4.2.2 自配鋯/鈦化成液配置 57 4.2.3 電化學交流阻抗 58 4.2.4 動電位極化曲線 61 4.2.5 橫截面影像觀察 63 4.2.6 鹽霧試驗 67 4.3 添加陽離子對FZA化成之影響 69 4.3.1 添加陽離子之化成液配置 69 4.3.2 表面形貌與橫截面之影像觀察 71 4.3.3 電化學交流阻抗 82 4.3.4 動電位極化曲線 87 4.3.5 成膜機制討論 91 4.4 添加氟離子對FZA化成之影響 95 4.4.1 添加氟離子之化成液配置 95 4.4.2 腐蝕行為分析 96 4.4.3 橫截面影像觀察 99 4.4.4 XPS成份分析 101 4.4.5 成膜機制討論 104 5 第五章 結論 106 參考文獻 108 | |
dc.language.iso | zh-TW | |
dc.title | 6061鋁合金之鋯酸化成處理與腐蝕行為研究 | zh_TW |
dc.title | The Corrosion Behavior of Hexafluorozirconic Acid Conversion Coating on 6061 Aluminum Alloys | en |
dc.type | Thesis | |
dc.date.schoolyear | 108-2 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 蔡文達(Wen-Da Tsai),汪俊延(Jiun-Yan Wang),葛明德(Ming-De Ge),林景崎(Jing-Chi Lin) | |
dc.subject.keyword | 6061鋁合金,鋯化合物化成處理,微結構,電化學交流阻抗,鹽霧試驗, | zh_TW |
dc.subject.keyword | 6061 aluminum alloy (AA6061),zirconium conversion coating,microstructure,electrochemical impedance spectroscopy,salt spray test, | en |
dc.relation.page | 116 | |
dc.identifier.doi | 10.6342/NTU202002564 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2020-08-14 | |
dc.contributor.author-college | 工學院 | zh_TW |
dc.contributor.author-dept | 材料科學與工程學研究所 | zh_TW |
顯示於系所單位: | 材料科學與工程學系 |
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