本研究旨在利用自製氧化鈦/氧化鋁無機複合膜，進行同步電混凝/電過濾程序處理半導體廠之晶圓研磨廢水。首先，利用溶膠-凝膠法製備二氧化鈦漿液，並加入重量百分濃度為1 wt%的玉米澱粉溶液以形成浸鍍液，再利用浸漿成膜法將浸鍍液披覆於自製的管狀無機支撐體上，接著，高溫燒結以獲得氧化鈦/氧化鋁無機複合膜。將製備好之氧化鈦/氧化鋁無機複合膜以同步電混凝/電過濾程序處理晶圓廠之二種化學機械研磨廢水(水樣A為Cu-CMP廢水；水樣B為Mixed-CMP廢水)，並評估其濾液品質，研究亦討論出流水迴流與否對濾速及濾液品質之影響，最後探討不同逆洗時間與週期對薄膜濾速之影響。
研究結果顯示，當二氧化鈦漿液與玉米澱粉溶液體積比為3：1時，所製備出的薄膜孔徑會較大(15 nm)且薄膜厚度較厚(13 μm)。而在CMP廢水處理方面，隨電場強度增強，水樣A中銅離子與TOC去除率會逐漸上升，其他水質項目則無明顯之關係，在最佳的操作條件下，水樣A的濁度去除率可達到98%以上，而TOC去除率也可達90%以上，同樣地，水樣B的濁度去除率也有99%以上，濁度可降至1 NTU以下；而在出流水迴流與否操作程序方面，以出流水迴流最佳操作條件進行出流水不迴流實驗，水樣A之初始濾液通量分別為300 L/h•m2 (出流水迴流操作)和280 L/h•m2 (出流水不迴流操作)，水様B之初始濾液通量分別為360 L/h•m2 (出流水迴流操作)和370 L/h•m2 (出流水不迴流操作)；而在濾液品質方面，水樣A出流水迴流操作對總固體物含量、矽含量、銅離子、TOC和濁度去除率分別為71%、85%、72%、90%及99%，在出流水不迴流操作方面，固體物含量、矽含量、銅離子、TOC和濁度去除率分別則分別為68%、88%、78%、90%及99%；水樣B出流水迴流操作對總固體物含量、矽含量、TOC和濁度去除率分別為76%、84%、78%及99%，在出流水不迴流操作方面，總固體物含量、矽含量、TOC和濁度去除率分別為78%、86%、72%及99%。從上述結果來看，出流水迴流操作與否對濾液通量及濾液品質的影響並無明顯之關係存在；但在濾液品質方面可適用於灌溉用水及循環式冷卻補充水；另外在逆洗週期與頻率方面，發現經由規律的反沖洗可降低薄膜阻塞的現象，且經由逆洗程序也可延長薄膜使用壽命。

In this study, two types of chemical mechanical polishing wastewaters (designated Cu-CMP wastewater and mixed-CMP wastewater, respectively) from a wafer fabrication plant was treated by a simultaneous electrocoagulation/electrofiltration (EC/EF) process using laboratory-prepared TiO2/Al2O3 composite membranes. First, tubular membrane supports of Al2O3 were prepared by the extrusion method. Then the slip composed of nanoscale TiO2 (prepared by sol-gel process) and 1 wt% of corn starch was applied on the aforementioned tubular membrane supports by the dip-coating method, followed by sintering to obtain tubular TiO2/Al2O3 composite membranes. These tubular inorganic composite membranes then were incorporated into an EC/EF treatment module for the treatment of CMP wastewaters. The permeate qualities were evaluated. In addition, the effects of different operating modes (i.e., the flow-through mode and recirculation mode) on membrane flux and permeate quality were conducted. Finally, the effects of changing the backwash time and backwash cycle on the membrane flux were also investigated.
Experimental results have shown that the slip containing 75 v/v% of TiO2 sol and 25 v/v% of corn starch solution would yield a membrane layer with a thickness of 13 μm and a pore size of 15 nm. On the CMP wastewater treatment, the removal efficiencies of copper ion and total organic carbon (TOC) were found to increase with the increasing electric field strength. This relationship, however, did not apply to other water quality items. Under the optimal operating conditions of using the recirculation mode, the removal efficiencies for turbidity and TOC for Cu-CMP wastewater were determined to be 98% and 90%, respectively. Similarly, a turbidity of < 1 NTU (a removal efficiency of 99%) was obtained for mixed-CMP wastewater. By using the same optimal operating conditions for the recirculation mode to treat Cu-CMP wastewater, initial fluxes of 300 L/h•m2 and 280 L/h•m2 were obtained for the flow-through mode and recirculation mode, respectively. The corresponding initial fluxes for mixed-CMP wastewater were 370 L/h•m2 and 360 L/h•m2, respectively. For the case of the recirculation mode, the removal efficiencies of total solids content, silicon, copper ion, TOC, and turbidity for Cu-CMP wastewater were 71%, 85%, 72%, 90% and 99%, respectively. The corresponding removal efficiencies of 68%, 88%, 78%, 90% and 99%, respectively were determined for the case of the flow-through mode. On the other hand, the removal efficiencies of total solids content, silicon, TOC, and turbidity for mixed-CMP wastewater using the recirculation mode were 76%, 84%, 78% and 99%, respectively; whereas 78%, 86%, 72% and 99%, respectively for the flow-through mode. Based on the above findings, the operating mode is not a significant parameter in influencing the membrane flux and quality. Permeate obtained in this work was found to be recyclable for the use in irrigation and make-up water for cooling towers. Backwashing was found to be important to the membrane flux in this study.

聲明切結書 i
謝誌 ii
摘要 iii
Abstract v
目錄 vii
表目錄 xii
圖目錄 xiii
照片目錄 xv
第一章 前言 1
1.1 研究緣起 1
1.2 研究目的 2
1.3 研究項目 3
第二章 文獻回顧 6
2.1 化學機械研磨製程簡介 6
2.1.1化學機械研磨技術 6
2.1.2 CMP硬體設備與操作流程 7
2.1.3 CMP製程研磨液特性與種類 7
2.1.4 CMP製程廢水及其處理技術 8
2.2 電混凝 14
2.2.1 電混凝基本原理 14
2.2.2 電混凝程序之相關研究 16
2.3 薄膜單元 18
2.3.1薄膜定義與特性 18
2.3.2 薄膜分離程序 18
2.3.3 薄膜組件之形式 20
2.4 薄膜程序過濾方式 22
2.4.1掃流薄膜電過濾 23
2.5 無機薄膜介紹 25
2.5.1 無機薄膜特性 25
2.5.2 管狀無機濾膜之應用 25
第三章 實驗材料、設備與方法 27
3.1 實驗材料 27
3.1.1 化學機械研磨廢水 27
3.1.2 其它試藥及材料 27
3.2 實驗設備 29
3.2.1 蒸氣壓氣體滲透偵測裝置 29
3.2.2 同步電混凝/電過濾處理模組裝置 29
3.2.3 其他設備及儀器 31
3.3 實驗方法 32
3.3.1 管狀無機濾膜之製備 32
3.3.2同步電混凝/電過濾處理系統之操作 33
3.3.2 同步電混凝/電過濾處理模組之濾膜逆洗 35
3.4 管狀無機膜性質分析 35
3.4.1 掃描式電子顯微鏡 35
3.4.2 管狀無機濾膜之孔徑分布測定 36
3.4.3 阻截分子量測定 36
3.5 CMP廢水、濾液品質分析方法 37
第四章 結果與討論 38
4.1 管狀無機複合膜製備及性質分析 38
4.1.1 過濾層厚度 38
4.1.2 孔徑分佈 41
4.1.3 阻截分子量 43
4.2 廢水基本性質分析 45
4.2.1 顆粒粒徑分析 45
4.2.2 掃描式電子顯微鏡-能量分散光譜分析(SEM-EDS) 46
4.2.3 顆粒界達電位之量測 49
4.2.4 其它水質項目特性分析 51
4.3 同步電混凝/電過濾處理模組之操作條件探討 53
4.3.1 電場強度對濾液通量及濾液品質之影響 53
4.3.2 理論臨界電場強度 59
4.3.3 過濾壓差對濾液通量之影響 59
4.3.4 掃流速度對濾液通量之影響 62
4.3.5最佳操作條件對CMP廢水之處理效果 65
4.4出流水迴流與否對濾液通量之影響及濾液品質分析 67
4.5逆洗週期與逆洗時間 72
第五章 結論與建議 75
5.1 結論 75
5.2建議 76
參考文獻 77
碩士在學期間發表之學術論文 89

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