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研究生： 蔡明瑞
Ming-jui Tsai
論文名稱： 電漿和網版印刷鍍膜材料表面改質
Surface Modification of Material by Plasma and Screen-Printing Coating
指導教授： 李雄
Shyong Lee
口試委員:
學位類別： 博士
Doctor
系所名稱： 工學院 - 機械工程學系
Department of Mechanical Engineering
畢業學年度： 98
語文別： 中文
論文頁數： 111
中文關鍵詞： 高功率脈衝磁控濺鍍 、類鑽碳膜 、網版印刷 、連接板 、過濾式陰極真空電弧
外文關鍵詞： FCVA, HIPIMS, DLC, Screen printing, Interconnect
相關次數： 點閱：10  下載：0 
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    • 本研究使用電漿和網版印刷方法鍍膜進行材料表面改質。電漿鍍膜法採用過濾式陰極電弧法(FCVA)和高功率脈衝磁控濺鍍法(HIPIMS) 以鈦金屬為陰極、C2H2為反應氣體，在SKH51和WC基材表面被覆含鈦類鑽碳膜(Ti-C:H)，進行基材表面降低摩擦係數和磨耗性之表面改質。
    FCVA製程以基材偏壓和靶電流的變化為實驗參數，而HIPIMS以基材偏壓和基材至靶距離為實驗參數。鍍膜之化學成份、外觀形貌、微結構、機械性質和磨耗性質等分別使用輝光放電分光儀、掃描式電子顯微鏡、拉曼光譜儀、X光繞射儀、 X光電子光譜儀、奈米壓痕儀、磨耗機和刮痕機等量測設備進行分析，量測結果顯示Ti-C:H膜表面光平，平均摩擦係數低於0.1、磨耗率為10-17 m3/Nm及附著力大於5 kg，鍍膜對基材表面摩擦潤滑性有明顯改善。
    另一個研究主題係使用網版印刷法被覆LSCF、LSM塗層在固態燃料電池之Crofer22 APU連接板上，在800 ℃之氧化氣氛處理200小時，結果顯示塗層能抑制Cr元素從Crofer22 APU連接板擴散出，塗層之ASR (area-specific resistance ；ASR)值以LSCF較LSM為低。

    This study was to modify surface of material by Plasma and screen-printing coating. One of the study issue was that Ti-containing amorphous hydrogenated carbon (Ti-C:H) thin films were deposited on SKH51 and WC substrates by filtered cathodic vacuum arcing (FCVA) and high power pulse magnetron sputtering (HIPIMS) in order to reduce friction coefficient and wear rate. The Ti-C:H thin films deposition used the mixture of Ar and C2H2 gases atmosphere with the titanium metal as cathodic materials. Furthermore, the effects of substrate bias, target current and substrate-to-target distance on film properties have been studied from FCVA and HIPIMS coating system. The film properties including composition, morphology, microstructure, mechanical and tribological characterizations were investigated by glow discharge spectroscopy (GDS), scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Nanoindenter and pin-on-disk tribometer, respectively. As a result, the surface of films was smooth, mean coefficient of friction was less than 0.1, wear rate was 10-17 m3/Nm, and critical load was more than 5 kg.
    Moreover, the screen-printing method also was investigated in the study. The LSCF and LSM films were applied on a Crofer22 APU interconnect for solid oxide fuel cells (SOFC) by screen-printing method. It was then tested in a simulated oxidizing environment, 800 ◦C for 200 h. The results showed that the LSCF film can change the oxidation behavior of Crofer22 APU. Moreover, long-term electrical resistance measurement also indicated that area-specific resistance (ASR) of the alloy with LSCF coating film is significantly lower than that of the LSM coating.

    中文摘要 i 英文摘要 ii 誌謝 iii 目 錄 iv 圖 目 錄 viii 表 目 錄 xii 第一章 緒 論 1 1.1 電漿被覆含鈦類鑽碳膜 1 1.2 網版印刷陶瓷膜在SOFC連接板 3 1.3 論文大綱 6 第二章 理論基礎 7 2.1電漿生成 7 2.2含氫類鑽碳膜之介紹 8 2.3 類鑽碳膜(DLC)成長理論 12 2.4 類鑽碳膜(DLC) 成長技術 15 2.5鍍膜的殘留應力 19 2.6改善類鑽碳鍍層附著力的方法 19 2.7添加金屬於鍍膜內 20 2.8適當熱處理 20 2.9 離子轟擊效應 20 2.10類鑽碳膜之熱穩定性 21 2.11 碳氫氣體選用 22 2.12 偏壓 23 2.13 碳化物 24 第三章 過濾式陰極真空電弧被覆含鈦類鑽碳膜 25 3.1過濾式陰極真空電弧製程 25 3.2 陰極點形成微坑機制 28 3.3 電荷狀態 28 3.4 離化反應 28 3.5 實驗設備 29 3.6電漿穿透率 33 3.7實驗方法步驟 35 3.7.1 試片準備與清潔 36 3.7.2 鍍膜步驟 36 3.7.3 量測分析 40 3.8結果與討論 41 3.8.1膜組織成份分析 41 3.8.2 鈦含量與沈積率 42 3.8.3 XPS (X-ray photoelectron spectroscopy)分析 44 3.8.4 X光繞射分析(XRD) 48 3.8.5奈米硬度壓痕測試(Nanoindenter) 49 3.8.6 磨潤測試 51 3.8.7 磨耗率 53 3.8.8 附著力測試 55 3.9 小結 56 第四章 高功率脈衝磁控濺鍍被覆含鈦類鑽碳膜 57 4.1 高功率脈衝磁控濺鍍 57 4.2實驗設備與方法 58 4.2.1 實驗設備 58 4.2.2 試片準備與清潔 59 4.2.3 實驗製程 59 4.2.4 分析方法 60 4.3 結果與討論 65 4.3.1 成份分析 65 4.3.2 沈積速率 67 4.3.3 X光繞射分析 67 4.3.4 拉曼光譜分析 68 4.3.5 奈米硬度測試 71 4.3.6 附著力測試 73 4.3.7 磨潤性測試 76 4.4 小結 78 第五章 固態氧化物燃料電池連接板網印陶瓷膜改質 79 5.1 基本理論 79 5.1.1 固態氧化物燃料電池之基本原理 79 5.1.2 固態氧化物燃料電池構造及特性 80 5.1.3 陽極 81 5.1.4 電解質 81 5.1.5 陰極 82 5.1.6 連接板 82 5.1.7 金屬連接板表面處理 83 5.2 實驗方法與設備 86 5.2.1 網印LSCF和LSM漿料製作 86 5.2.2 網印LSCF和LSM膜試片製作 86 5.2.3 量測設備 87 5.2.4 高溫電阻量測Area specific resistance(ASR) 87 5.3 結果與討論 91 5.3.1 氧化表面x光繞射分析 91 5.3.2 LSCF和LSM塗層表面組織分析 91 5.3.3 LSCF/Crofer22 APU界面元素擴散分析 92 5.3.4 高溫氧化測試 93 5.4 小結 99 第六章 結 論 101 參考文獻 103 表 目 錄 表2-1：陰極電極不同靶材射出之離子能 23 表3-1: FCVA製程參數 38 表5-1: 塗層被覆方法 85 表5-2 : Crofer22 APU合金化學組成 (wt. %). 90 圖 目 錄 圖2-1: 電漿示意圖；圖(a)電壓對電流關係，圖(b)直流電漿 8 圖2-2：碳結構；(a)石墨晶體，(b)鑽石晶體 11 圖2-3：鑽石、石墨與carbon 分別具備SP3、SP2 與 SP1 之結構 12 圖2-4：非晶質含氫類鑽碳膜；(a)結構圖，(b)三元相圖 12 圖2-5：脫氫反應及壓縮將sp2轉換成sp3 15 圖2-6：離子沉積 16 圖2-7：離子濺射 17 圖2-8：脈衝分子雷射 17 圖2-9：PECVD 17 圖2-10：離子束輔助沉積 18 圖2-11：陰極電弧電漿系統 18 圖2-12：封閉場非平衡磁控濺射 18 圖2-13：不同碳氫氣體之沉積速率與離化電壓之關係圖 23 圖3-1: FCVA之離子能分佈 26 圖3-2: 陰極表面形成電漿射出正離子及熔融微滴示意圖 26 圖3-3: 陰極靶電漿流示意圖 27 圖3-4：真空陰極電弧放電離子鍍系統所產生之微粒(右圖為斷面圖) 27 圖3-5 : 過濾式陰極真空電弧法設備；(a)電源線路圖 29 圖3-5 : 過濾式陰極真空電弧法設備；(b)真空腔體圖，(c)磁濾管圖 30 圖3-6 : 過濾式陰極電弧零組件示意圖 31 圖3-7: FCVA管道內置濾片示意圖 32 圖3-8: FCVA管道電漿穿透率量測示意圖 34 圖3-9: FCVA被覆Ti-C:H膜實驗流程圖 35 圖3-10: 含鈦類鑽碳膜結構示意圖 37 圖3-11: 試片輝光與轟擊 37 圖3-12: 直流脈衝偏壓波型(350KHz, 60% Duty) 38 圖3-13: FCVA被覆含鈦類鑽碳膜試件；(a)水龍頭陶瓷磨片、碳化鎢和SKH51 ，(b)PCB微銑刀(直徑2mm) 39 圖3-14: 鈦靶陰極電弧放電後表面和電漿場景 39 圖3-15: 直徑2mm PCB微銑刀被覆類鑽碳膜；(a)陰極電弧被覆，(b) 陰 極電弧被覆放大圖，(c) FCVA被覆視圖，(d) FCVA被覆視圖 40 圖3-16: 含鈦類鑽碳膜縱向成份分佈圖 41 圖3-17 : 偏壓與鈦含量、沈積率之關係曲線 43 圖3-18 : 靶電流與鈦含量、沈積率之關係曲線 43 圖3-19 : 含鈦類鑽碳膜鍵結能譜圖 45 圖3-20 : C1s能譜之sp3、sp2含量分析 46 圖3-21 : 偏壓與sp3/sp2 關係曲線圖 46 圖3-22 : Ti2p能譜分析 47 圖3-23 : 靶電流與sp3/sp2 關係曲線 47 圖3-24 : Ti-C:H膜X光繞射譜(入射角3°) 48 圖3-25 : 偏壓參數之硬度與深度關係曲線圖 50 圖3-26 : 硬度、楊氏模數與偏壓參數之關係曲線 50 圖3-27 : 含鈦類鑽碳膜奈米硬度與靶電流關係曲線 51 圖3-28 : (a)磨耗試驗機 (b)磨痕軌跡 52 圖3-29 : 未被覆類鑽碳膜試片磨耗測試之摩擦係數與圈數關係 52 圖3-30 : 偏壓與摩擦係數之關係曲線 53 圖3-31 : 磨痕斷面曲線量測設備 54 圖3-32 : 偏壓與磨耗率關係曲線 54 圖3-33 : 附著力刮痕測試之刮痕 55 圖3-34 : 偏壓與Lcr2刮痕臨界作用力之關係曲線 56 圖4-1: 高功率脈衝磁控濺鍍Ti-C:H膜實驗流程圖 61 圖4-2: 高功率脈衝磁控濺鍍系統設備圖 62 圖4-3: 高功率脈衝磁控濺鍍系統配線圖 62 圖4-4: 磁場Bz強度與靶面法向量距離之變化曲線 63 圖4-5: 靶和基材之脈衝電壓、電流曲線 63 圖4-6: HIPIMS被覆試件:(a) Ti-C:H膜試片(b)軸承環零件(c)捨棄式刀片 鍍TIN膜用於無鉛銅切削 64 圖4-7: 原子與深度之關係曲線圖 65 圖4-8a: Ti含量、基材距靶距離和偏壓關係曲線 66 圖4-8b: Ti含量、基材距靶距離和偏壓關係曲線 66 圖4-9: Ti-C:H在SUS304基材沈積成長速率 67 圖4-10: Ti-C:H膜X光繞射譜 68 圖4-11: Ti-C:H膜之拉曼光譜 69 圖4-12: 偏壓與I(D)/ I(G)比值之關係曲線 70 圖4-13: 偏壓與G band position之關係曲線 70 圖4-14: 偏壓與硬度之關係曲線圖 72 圖4-15: 偏壓與楊氏模數之關係曲線圖 72 圖4-16: 含鈦類鑽碳膜被覆在WC之刮痕破壞痕跡 74 圖4-17: 偏壓與臨界負載之關係曲線 74 圖4-18: 偏壓與臨界負載之關係曲線 75 圖4-19: 不銹鋼基材刮痕測試 75 圖4-20: 基材偏壓與摩擦係數關係 76 圖4-21: 磨耗測試之磨痕軌跡 77 圖4-22: 磨耗測試之磨凹曲線 77 圖5-1 : 固態氧化物燃料電池工作原理圖 79 圖5-2 : 單電池組之固態氧化物燃料電池結構圖 80 圖5-3 : SOFC電池堆示意圖(核研所燃材組1 kW SOFC) 81 圖5-4 : SOFC金屬連接板毒化陰極模型 84 圖5-5 : 網印法示意圖 85 圖5-6 : 塗覆LSM和LSCF膜實驗流程 89 圖5-7 : LSM和LSCF塗覆試片燒結流程 90 圖5-8 : 金屬連接板氧化皮膜的ASR量測方式示意圖 90 圖5-9 : LSCF塗佈在Crofer22 APU基材之X光繞射比較；圖(a) 1050℃ 燒結50分鐘，圖(b) 1050℃燒結50分鐘，再置於800℃之大氣 氣氛200小時 93 圖5-10 : LSM塗覆於Crofer22 APU基材，經高溫燒結與高溫燒結後再 經氧化處理之X光繞射圖比較 94 圖5-11 : (a) LSCF塗層，(b) LSM塗層燒結後表面形貌。LSCF塗層 1050℃、50分鐘，LSM塗層1100℃燒結90分鐘 94 圖5-12 : (a) LSM塗層，(b) LSCF塗層，經燒結後再經800℃高、200 小時氧化處理之像圖和成份分析 95 圖5-13 : LSCF/Crofer22 APU燒結後，再經800℃空氣氧化200小時後； (a)高溫氧化之截面圖與(b) EPMA定量 96 圖5-13 : LSCF/Crofer22 APU燒結後，再經800℃空氣氧化200小時後； (c) EPMA元素濃度分佈圖 97 圖5-14 : Crofer22 APU/LSCF於800°C高溫氧化300小時之(a) BEI 影像(b)EPMA元素線掃描分析結果 98 圖5-15 : LSM與LSCF塗上Crofer22 APU的ASR值與時間的關係圖 99

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