臺灣博碩士論文加值系統

表面處理技術之無電解鎳在工業上有諸多耐腐蝕領域的應用，儘管本項技術之發展已超過60年，鋁及鋁合金上析鍍無電鍍鎳之無孔薄膜鍍層依然面臨挑戰，因鋁表面易生成致密氧化物Al2O3，施加表面處理容易使鍍層形成缺陷。
本研究分四個部分逐一進行探討，第一、為鋁合金前處理採用HNO3在常溫下進行酸浸蝕8分鐘，採用SEM觀察腐蝕的情形及EDS定性檢測殘留元素。第二、探討二次鋅置換法備製置換層，採用SEM觀察Zn晶粒分佈形貌。第三、探討濺鍍法備製置換層，藉此探討濺鍍法和選用鋅靶材之可行性，採用SEM觀察鋅薄膜表面結晶組織及EDS定性檢測薄膜元素。第四、探討不同表面粗糙度之鍍層對結合力和耐腐蝕性的影響。經實驗探討後，前處理採用丙酮除油質、NaOH鹼洗、HNO3酸浸蝕，每道流程之間要加強超音波震盪，經流程後可得到乾淨且適合無電鍍的試片。二次鋅置換法經SEM觀察發現剝鋅形成的蝕孔區域為鋅晶粒成核點，提供第二道浸鋅反應位置和界面間結合性，再經結合力與耐腐蝕測試，發現二次鋅置換法最佳的反應時間為第一道浸鋅40秒、剝鋅10秒，第二道浸鋅30秒。本研究證明採用濺鍍法沉積薄膜的可行性，經測試發現鋅金屬並不適合作為置換層的材料，經耐腐蝕測試發現表面粗糙度Ra值太低，表面不能提供適當結合力，造成鍍層與基材結合力不足，會明顯影響耐腐蝕性。

Surface treatment of electroless nickel in the industry has many applications in the field of corrosion-resistant, although this technology development has more than 60 years, aluminum and aluminum alloy plating on the no-pore of film coating of the electroless nickel is still facing challenges, the aluminum surface generate dense oxide Al2O3, not on easy to the surface treatment and deal with defects such as the formation of coating for example: pores, tumors, sparkling, exfoliate.
The study is divided into four sections :pre-treatment of aluminum alloy aluminum substrate acid etching of the impact .Use a neutral detergent to remove the mechanical processing of oil, acetone ultrasound shock, ultrasound washed, 10 wt% NaOH 15 ℃ cleaning about 30 seconds, washed ultrasound, 15 wt% HNO3 at room temperature for acid etching three minutes, five minutes, seven minutes, eight minutes. Using SEM & EDS & AFM observation of aluminum sheet metal corrosion by the situation. EDS detection by residual elements of aluminum.
Aluminum of secondary zincate by formation of zinc film of the discussion. To two soaking zincate and zinc stripping. The second road soaking zincate set to 10 seconds, 30 seconds, 50 seconds of reaction time, and the electroless plating. Using SEM& AFM observation 2-D and 3-D appearance of the grain distribution of Zn.Determination of its corrosion resistance and combination of force.
Discussion of aluminum sheet metal used by the system of sputtering zinc film. To explore sputtering law and the choice of the feasibility of zinc materials. Experimental methods used to establish the pre-treatment cleaning of aluminum, into the RF magnetron sputtering machine splash zinc film, and the electroless nickel plating. Using SEM&EDS observation of the surface film of zinc crystal structure and composition of film ratio. Determination of its corrosion resistance and combination of force.The coating of corrosion resistance and combination of force on the surface roughness of the combination of the impact. Aluminum processing method will be different surface roughness in the same specimen (polished surface, NO.1200 grinding face, NO.600 grinding face) pre-processing, secondary Zincate, electroless nickel plating. In the treatment before and after the electroless nickel plating. Aluminum specimens measuring surface roughness,using SEM observe the coating surface roughness and cross-sectional thickness of coatings, determination of its corrosion resistance and combination of force.
The four-part study, received pre-treatment the cleaning process using acetone ultrasound shock, ultrasound washed, 10wt% NaOH in 15 ℃ cleaning about 30 seconds, washed ultrasound, 15wt% HNO3 at room temperature for 8 minutes for the etching acid of the best parameters, and to take every road between the processes to strengthen ultrasound washed shocks, can be no excessive corrosion and Al-rich elements of the specimen.
Aluminum of secondary zincate by SEM & AFM observed that the formation of zinc stripping the pit, Reaction of the second road soaking zincate film and the aluminum substrate of the interface between the light of combination of force, To the combination of force and corrosion resistance test, found second zincate of zinc films, the best reaction time - the first road soaking zincate 40 seconds, 50wt% HNO3 zinc stripping 10 seconds, the second road soaking zincate 30 seconds.
Study shows that a sputtering reaction sediments of the law is feasible, but after tests found that zinc material is not suitable for the reaction of the material. The tests found that the corrosion-resistant surface roughness Ra value too low and too flat surface, the combination of insufficient coating, will significantly affect corrosion resistance.

中文摘要 Ι
英文摘要 II
誌謝 III
目錄 IV
表目錄 VII
圖目錄 VIII

第一章 緒論1
1.1 前言1
1.2 研究動機2
1.3無電鍍鎳特色與應用2
1.4無電鍍鎳技術與發展3
1.5 論文架構4

第二章 文獻回顧與理論基礎5
2.1 理論基礎5
2.1.1 無電鍍鎳5
2.1.2 無電鍍鎳的反應機構6
2.1.3 無電鍍鎳鍍層特性6
2.1.4 置換層製作7
2.1.5 電雙層效應8
2.2 鋁合金腐蝕的類型介紹11
2.3 文獻回顧13

第三章 實驗方法17
3.1 實驗目的17
3.1.1 試片備製17
3.1.2 前處理21
3.2 實驗步驟與分析22
3.2.1探討鋁合金前處理對鋁基材浸蝕的影響22
3.2.2 探討二次鋅置換法沉積薄膜對鍍層性能的影響24
3.2.2.1 無電鍍鎳製程介紹26
3.2.3 探討濺鍍法備製置換層結晶組織對鍍層性能的影響30
3.2.4 表面粗糙度對鍍層的耐腐蝕性與附著力的影響32

第四章 實驗結果與討論34
4.1 探討鋁合金前處理的酸浸蝕對鋁基材的影響34
4.1.1 表面形貌觀察34
4.1.2 EDS定性分析37
4.2 探討二次鋅置換法備製置換層結晶組織對鍍層性能的影響38
4.2.1 表面形貌觀察38
4.2.2 AFM掃瞄分析42
4.2.3 結合力分析44
4.2.4 耐腐蝕性分析45
4.3 探討濺鍍法備製置換層結晶組織對鍍層性能的影響47
4.3.1 SEM/EDS分析47
4.3.2 結合力分析50
4.3.3 耐腐蝕性分析52
4.4 探討鋁合金表面粗糙度對鍍層的耐腐蝕性與結合力的影響53
4.4.1 表面粗糙值量測53
4.4.2 表面形貌觀察54
4.4.3 鍍層厚度量測55
4.4.4 EDS定性分析56
4.4.5 結合力分析56
4.4.6 耐腐蝕性分析58

第五章 總結60
5.1 結論60
5.2 未來展望61

參考文獻62
個人資料65

[1]Lowenheim, F. A., 1970, ”Modern Electroplating, Third Edition”, J. Wiley and Sons, Inc, New York, pp.591, pp. 710.
[2]O'Sullivan, E. J., et al, 2002, ”Advances in Electrochemical Science and Engineering”, vol.7, Wiley-VCH, Wenham, pp. 225.
[3]易鍍網http://www.enease.com/jnchu-yingyong.htm
[4]胡文彬等人，2003，難鍍基材的化學鍍鎳技術，化學工業出版社，北京，頁3-5。
[5]Keong, K. G., et al, 2003, “Hardness Evolution of Electroless Nickel-Phosphorus Deposits with Thermal Processing”, Surface and Coating Technology,Vol. 168, lssues 2-3, pp. 263-274。
[6]Goldenstein A.W., et al, 1957, ”Electrochem. Soc.”, Vol. 104, pp. 104.
[7]陳宏生，謝淑惠，楊聰仁，2000，”銅無電鍍鎳熱處理後在3.5wt % NaCl抗蝕性研究”，防蝕工程，第十四卷，第四期，頁1-8。
[8]易鍍網 http://www.enease.com/jnchu-xingneng.htm
[9]Paul R., P. Buisson, N. Joseph, 1952, Ind. Eng. Chem, Vol. 44, pp. 1006.
[10]王裕淵，謝銘郎，”鏡面加工之無電鍍鎳技術”，機械工業雜誌，第249期，頁224~231.
[11]Hewitson E.H., 1927, ”Eastman Kodak Co”, U.S. Pat.1 627 900.
[12]Straumanis M.E.,et al, 1949, ”Electrochem. Soc.”, Vol. 95, pp. 98.
[13]Streicher M.A., 1948;1949, J. Electrochem. Soc., Vol. 93, pp. 285；Vol. 96,
pp. 170.
[14]Korpium, J., et al, 1939, U.S. Pat. 2 142 564.
[15]莊達人，2006，VLSI製造技術-六版，高立出版，台北，頁151。
[16]Duncan. J. S. , 2001，膠體及界面化學入門，張有義、郭蘭生譯，高立出版 : 新科技總經銷，台北。
[17]田福助，1996，電化學-理論與應用，新科技書局，台北市，頁435~451。
[18]孫立杰，2004，水溶液中溶氧對金屬腐蝕的影響，逢甲大學，碩士論文。
[19]陳天佑，2002，無電鍍鎳表面處理對7075-T6鋁合金耐候性與疲勞強度之研究，大同大學，碩士論文。
[20]Gao J., et al, 2006, “Electroless Ni-P-SiC Composite Coatings with Superfine Particles,” Surface and Coatings Technology, pp. 5836-5842。
[21] Mallory G. O., 1985, ”Plat. Surf. Finish.”, Vol. 72, pp. 6.
[22] Azumi K. T., et al, 2003, ”Electrochem. Soc.”, Vol. 150, pp. C461.
[23] Lashmore D S, et al, 1980, ”Immersion Coating on Aluminium”, Plating & Surface Finishing, Vol. 67, pp. 37~41.
[24] K.L. Lin, et al, 1996, ”The morphologies and the chemical states of the multiple
zincating deposits on Al pads of Si chips”, Thin Solid Films, Vol. 288, pp. 36.
[25]周孟鋒，2002，複合金屬粉末之製備與應用，逢甲大學，碩士論文。
[26]Abdel Hamid Z., M.T. Abou Elkhair, 2002, ”Development of electroless nickel-phosphorous composite deposits for wear resistance of 6061 aluminum alloy”, Material Letters 57, pp. 720-726.
[27]馮立明，王月，王玉景，2005，”6063鋁合金化學鍍Ni-P合金工藝研究”，腐蝕與防護，第26卷，第2期，2月。
[28] Armyanov S. M., 1992, ”Electroless Nickel-Phosphorus Deposition on Aluminum”, Interface and Internal Stress Metal Finishing, Vol. 90, pp. 36~41.
[29]李傳英、黃尊禧等人，2002，”以無電鍍法於氮化物障礙層上沉積金屬導線的方法”，台灣專利.512185。
[30]姜曉霞，沈偉，2000，化學鍍理論及實踐，國防工業出版社，北京。
[31]葉宏耀，2004，摩擦面溫度量測與研究，國立高雄應用科技大學，碩士論文。
[32]維基百科http://zh.wikipedia.org/wiki/6061%E9%93%9D%E5%90%88%E9%87
%91#.E6.87.89.E7.94.A8
[33]潘復生，張丁非，2006，鋁合金及應用，化學工業出版社，北京，頁220~242。
[34]王志方，1988，材料表面測定技術，復漢出版社，台南市，頁17。
[35]魏坤霞等人，2007，”超細晶鋁合金化學鍍鎳研究”，表面技術，第36卷，
第1期，頁48~50。
[36]胡文彬，劉磊等著，2003，難鍍基材化學鍍鎳技術，北京化學工業出版社，
頁58~60。
[37]維基百科http://zh.wikipedia.org/wiki/%E7%A1%9D%E9%85%B8
[38]王志方，1988，材料表面測定技術，復漢出版社，台南市，頁98-99。
[39] http://elearning.stut.edu.tw/caster/3/no5/5-2.htm
[40]吳泰伯，許樹恩，2006，X光繞射原理與材料結構分析，中國材料科學學會，新竹市，頁522。
[41]http://cslin.auto.fcu.edu.tw/eleme/premea/lesson3-3-1.htm
[42]Golby, J.W. and Dennis, J.K., “A study of the effect of pretreatment on the
plating of aluminum alloys”, Surf. Technol., 12, (1981) 141.
[43]涂撫洲，蔣漢瀛，2000，”鋁輪轂電鍍”，電鍍與塗飾，第19卷，第1期，頁19~23。
[44]P. Sampath Kumar, P. Kesavan Nair, 1994, ”Effect of phosphorus content
on the relative proportion of crystalline and amorphous phases in electroless Ni-P deposit”, Journal of Materials Science Letters, Vol. 13, pp. 671-674.