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研究生:張威閔
研究生(外文):Wei-Min Chang
論文名稱:電鍍鎳層之粗糙度對不鏽鋼之CVD碳膜的影響
論文名稱(外文):Effect of Roughness of Electroplating Ni Layer on Carbon Film-Coated Stainless Steel Grown by Chemical Vapor Deposition
指導教授:陳士堃
指導教授(外文):Shi-Kun Chen
學位類別:碩士
校院名稱:逢甲大學
系所名稱:材料科學所
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2009
畢業學年度:97
語文別:中文
論文頁數:95
中文關鍵詞:Ni層之表面粗糙度化學穩定性覆碳不鏽鋼板
外文關鍵詞:chemical stabilitySurface roughness (Ra) of the Ni layerCarbon film-coated stainless steel
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在質子交換膜燃料電池雙極板材料的應用中,覆碳不鏽鋼之成本和體積較石墨雙極板低和小,具有取代石墨雙極板的淺力。碳膜經由乙炔的熱裂解而形成,沉積在試片表面之裂解碳分子受到觸媒Ni催化作用的影響形成石墨碳層,Ni觸媒層藉由濺鍍方法製備。本研究製備Ni觸媒層的方法為成本較低、繞鍍性較佳之電鍍製程,使用的鍍液為Ni衝擊配方,並調變其電流密度及電鍍時間。接著利用化學氣相沉積法(CVD)沉積碳膜,反應溫度為750 oC,載體氣體(H2)與反應氣體(C2H2)的流量比為1.5。藉由FE-SEM和AFM觀察Ni層的表面形態、XRD確認其晶體結構;並利用FE-SEM觀察碳膜的表面形態、動電位極化法測試量測其抗蝕性。在Ni層膜厚固定為810 nm時,Ni層的表面粗糙度Ra值隨著電流密度由1增加至10 A/dm2而由31.9 nm降低至15.7 nm,在Ra = 15.7 – 18.4 nm 的Ni層其沉積出的碳膜為連續薄膜,而Ra = 16 nm 的Ni層沉積碳膜後具有最高之腐蝕電位(1.8 VRHE),此腐蝕電位高於高順向石墨之Ecorr (1.6 VRHE),因此推測Ni層的表面粗糙度為影響碳膜表面形態和化學穩定性的主要因素。
Carbon film-coated stainless steel (CFCSS) has been evaluated as substitute for graphite bipolar plate in polymer electrolyte membrane fuel cell (PEMFC), due to its low-cost and small-volume. The carbon film was synthesized by pyrolysis of acetylene. Pyrolytic carbon molecules form graphite carbon layer through the catalysis of Ni layer deposited by sputtering. In this study, Ni layer was prepared via electroplating due to the low-cost and superior-throwing power. Ni strike solution was chose for deposition, and the current density and electroplating time was manipulated in range of 1 – 10 A/dm2 and 15 – 1200 second, respectively. Carbon film was then deposited deposits at 750 oC under C2H2/H2 mixed gas ratio of 1.5 by CVD process. Surface morphology of the Ni layer was characterized by field emission scanning electron microscope (FE-SEM) and atomic force microscope (AFM). X-ray diffraction (XRD) was used to indentify crystal structure of the Ni layer. Morphology of the carbon film was analyzed by FE-SEM. Potentiostat was used to measure chemical stability of the carbon film. While thickness of the Ni layer fixed at 810 nm, the surface roughness (Ra) of the Ni layer was decreased from 31.9 nm to 15.7 nm with increasing current density of electroplating from 1 A/dm2 to 10 A/dm2. After CVD process, fibrous carbon layer was grown on the Ni layer. The fibrous carbon layer can not protect the metallic substrate from the attack of sulfuric acid. To obtain a continuous dense carbon film the Ra value of the Ni layer should be in the range from 15.74 nm to 18.41 nm. It appears that the surface roughness of the Ni layer play an important role for the structure and the resultant chemical stability of the carbon films. The highest value of Ecorr (1.8 VRHE) was obtained with Ra = 16 nm. The Ecorr value is even higher than that of highly oriented paralytic graphite (HOPG, 1.6 VRHE).
致謝……………….………………………………………………………I
中文摘要………………………………………………………………...II
英文摘要………………………………………………………………. III
目錄……………………………………………………………...…….. IV
圖目錄………………………………………………………………......IX
表目錄………………………………………………………..……….XIII
第一章、緒論……………………………………………………………..1
1-1 前言…………………………………………………………….....1
1-2燃料電池簡介……………………………………………………..1
1-3 燃料電池種類…………………………………………………….2
1-4 研究動機…………………………………………………..……...5
第二章、理論基礎與文獻回顧…………………………..………..……..7
2-1燃料電池研究背景…………………………..…………..………..7
2-1-1質子交換膜燃料電池操作原理……………...……………..7
2-1-2關鍵材料與元件……………………………..………..…….8
2-1-2-1質子交換膜…………….…….……..…………..….8
2-1-2-2觸媒層………………….………………….....…….9
2-1-2-3氣體擴散層…………….…………………..…...….9
2-1-2-4雙極板……………………..………….……….….10
2-1-2-4-1雙極板之特性需求……………..……..10
2-1-2-4-2雙極板之種類…………………..……..12
2-1-2-4-3金屬雙極板可信賴度之規範……..…..13
2-2電鍍技術…………………………………………………………14
2-2-1電鍍原理…………………………………..……………….14
2-2-2 影響鍍層之因素…..…………………..………………….17
2-3化學氣相沉積法…………………………………………………21
2-4碳…………………………………………………………………25
2-4-1催化石墨化…………………………………………..…….27
2-4-1-1觸媒原理……………………….…..……………..28
2-4-1-2觸媒催化石墨化機制……………...……………..29
2-4-2奈米碳球……….……………………..……………………33
2-4-2-1奈米碳球之形成機制……………………...….….33
2-4-2-2奈米碳球的製備方式…...……………………..…35
2-4-2-3奈米碳球之應用……………………………....….37
2-5腐蝕電化學………………………………………………………37
2-5-1金屬的腐蝕…………………………..…………………….37
2-5-2混合電位理論………………………………..…………….38
2-5-3 極化現象……………..…………………………………...39
2-5-4極化曲線……………………………………………….......41
第三章、實驗步驟與分析……………………………………..………..44
3-1實驗流程…………………………………………………………44
3-2基板前處理………………………………………………………44
3-2-1基板選擇……………………...…..………………………..44
3-2-2 基板之準備與清洗…………………………………..…...45
3-3沉積Ni層……………………………………………...........…....46
3-3-1 電鍍系統………………………………..…………..…….46
3-3-2 薄膜之沉積………………………………..……………...47
3-3-3 退火系統…………………………..…………………...…48
3-3-4 退火熱處理………………………..…………………...…49
3-4沉積碳膜…………………………………………………………49
3-5 薄膜特性量測與分析……………………………………...……51
3-5-1 膜厚量測………………………………………………...51
3-5-2 XRD結構分析…………………………………...………51
3-5-3 縱深成份分析……………………………………...……51
3-5-4 顯微組織觀察………………………………………...…52
3-5-5 原子力顯微圖像觀察……………………………...……52
3-5-6 化學穩定性量測……………………..………………..….53
第四章、結果與討論……………………………...…………………….56
4-1電鍍Ni層時間對沉積碳膜之影響…………………………...…56
4-1-1 Ni層初鍍膜之特性………………………….………….…56
4-1-1-1膜厚之量測………………………………....…….56
4-1-1-2結晶結構之分析…………………………....…….57
4-1-1-3表面形態之觀察…………………………..…..….59
4-1-1-4表面粗糙度之分析…………………………....….61
4-1-2碳膜之特性…………………………………….………..…62
4-1-2-1表面形態之分析……………………..………..….62
4-1-2-2 AISI 304 / Ni / C鍍層之縱深成份分析……….…66
4-1-2-3腐蝕性質之分析……………………..………...…68
4-1-3退火鎳層之特性…………………….…………………..…74
4-1-3-1結晶結構之分析………..……………………..….75
4-1-3-2表面形態之觀察…..…………………………..….76
4-1-3-3表面粗糙度之分析…………………………..…...77
4-2電流密度之影響…………………………………………………78
4-2-1 Ni層之特性………………….……………………….……79
4-2-1-2結晶結構之分析………………………………….79
4-2-1-3表面形態之觀察……………..……..…………….81
4-2-1-4表面粗糙度之分析………………..…..………….83
4-2-2碳膜之特性……………….………………………………..85
4-2-2-1表面形態之分析………………..…………..…….85
4-2-2-3 腐蝕性質之分析…………………………...….…87
第五章、結論…………………………………………………………....90
參考文獻……...……………………………………………..….………91
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