本研究利用溶膠凝膠法 (Sol-gel method)製備二氧化鈦膠體並將其被覆於碳鋼
(Carbon Steel, CS)以及氧化銦錫導電玻璃上(Indium tin oxide, ITO)，分別探討二氧化鈦被
覆在碳鋼與ITO上所呈現的腐蝕防制、光誘發表面親水性以及抗菌性等三種特性。首先，
在腐蝕防制部分，直接將二氧化鈦被覆於碳鋼表面，鍛燒過程中鐵離子會擴散進入二氧
化鈦薄膜內，使光催化效果降低，因此必須將碳鋼進行預長氧化膜處理，本實驗探討不
同預長氧化膜條件以及鍛燒熱處理的組合，讓二氧化鈦擁有良好結晶性的同時，鐵離子
也能有效被阻隔，實驗結果顯示最佳腐蝕防制參數為：碳鋼預氧化 600°C 維持 5 分鐘，
被覆二氧化鈦並熱處理 400°C 維持 60 分鐘，電位由-54mVAg/AgCl 降低到-263mVAg/AgCl，
電位變化為-210mV，電流密度由 1.24 x 10-8A/cm2 降低到 4.49 x 10-13 A/cm2，約 4 個數量
級。接著在光誘發表面親水性的部分，利用接觸角量測儀量測不同氧化膜之水接觸角，
再觀察被覆完二氧化鈦後的水接觸角，最後再照射紫外光探討二氧化鈦光催化表面親水
的性質，結果顯示被覆完二氧化鈦後，表面都變得比被覆前疏水，在照射紫外光下，水
接觸角會接近 0°，顯示此時極親水的現象 (Super-hydrophilic)。最後在抗菌性的部分，
首先觀察大腸桿菌(Escherichia coli, E.coli)在指定培養基生長的情形，每隔一段時間觀察
菌落形成單位 (Colony Forming Unit, CFU)，並繪製出生長曲線，結果顯示 0-1.5 小時為
潛伏期，1.5-7 小時為指數生長期，倍增時間(doubling time)約為 23 分鐘，7-24 小時為平
坦期，飽和 E.coli 菌液密度大約在 1-2 x 109 CFU/ml，到了 24 小時之後進入死亡期。接
著將生長曲線顯示之飽和 E.coli 菌液置於 ITO.TiO2、CS、CS.TiO2、control 等表面並搭
配 100%、10%、5%與 1% 強度之紫外光照射，探討細胞生存情形，繪製出存活曲線，
結果顯示紫外光強度降低會使細菌存數量上升，且在不同紫外光強度照射下，抗菌效果
由高至低依序皆為 ITO.TiO2、CS.TiO2、CS、Control。本研究成功利用溶膠凝膠法製備
出二氧化鈦，並能顯著地抑制腐蝕情形、紫外光照射下呈現完全親水以及一定程度的抗
菌性。

In this study, carbon steels (CSs) and Indium tin oxide (ITOs) with a titanium oxide(TiO2)
coating applied by the sol-gel method were investigated in three aspects, including preventing
or minimizing the atmospheric corrosion, photo-induced surface hydrophilicity and anti
bacterial properties. In the corrosion mitigation part, if TiO2 was directly coated on plain CS
and then annealed, the photocatalytic effect was poor. During the thermal treatment process,
iron atoms would diffuse from CS to TiO2 and limit the photocatalytic effect. Therefore, the
pre-oxidation process was necessary. Various oxide structures of carbon steel and the TiO2
thermal treatment process were investigated in this study. According to the experiment results,
the optimum processing parameter was pre-oxidizing on carbon steel at 600°C for 5 min,
coating TiO2 and then conducting thermal treatment at 400°C for 60min. Electrode potential
decreased from -54mVAg/AgCl to -263mVAg/AgCl, and the potential difference was -210mV .
Current density decreased from 1.237 x 10-8A/cm2 to 4.489 x 10-13 A/cm2 about four orders of
magnitude drop. In the photo-induced surface hydrophilicity part, we first used the sessile drop
method to measure the contact angle(CA) of different oxide films and we observed the CA of
TiO2 coated specimens and then measured the CA changes under UV illumination. These results
indicated that after coating the TiO2 on the pre-oxidized carbon steels, the CA increased while
under UV illumination the CA would decrease to almost 0°,which is a super-hydrophilic surface.
Last, in the anti-bacterial properties part, we first observed the Escherichia coli growth under
designated medium by measuring the colony forming unit (CFU) every a period of time and
draw a growth curve. Results showed that in the first 1.5h is lag phase, during 1.5-7 h is
exponential phase and doubling time is about 23 min, during 7-24h is stationary phase and the
maximum cell density of 1-2 x 109 CFU/ml is observed, after 24h is in dead phase. Then the
saturated E. coli bacteria solution (1-2 x 109) derived in the growth curve was placed on
different surfaces, i.e. ITO.TiO2, CS.TiO2, CS, Control, and irradiated with 100% and 10%


iii

intensity ultraviolet light (UV) to explore the viability of the cells and draw a survival curve.
These results reveal that no matter under 100% or 10% UV intensity the viable cell density
sequence from high to low was ITO.TiO2, CS.TiO2, CS, Control. This study concluded that the
titanium oxide prepared by the sol-gel method can significantly inhibit the corrosion behavior,
and it is completely hydrophilic under ultraviolet irradiation and has a certain degree of
antibacterial properties.

摘要 i
Abstract ii
致謝 iv
目錄 v
圖目錄 viii
表目錄 xiv
第一章 緒論 1
1.1 前言 1
1.2 研究動機 2
第二章 理論基礎 5
2.1腐蝕之電化學 5
2.1.1混合電位模型 (Mixed Potential Model, MPM) 5
2.1.2 電位-酸鹼圖 (E-pH diagram, Pourbaix diagram) 7
2.1.3 伊凡斯圖 (Evans Diagram)與極化曲線 (Polarization curve) 8
2.1.4 防蝕機制 11
2.2 表面能與接觸角 14
2.3 微生物學實驗 15
2.3.1 大腸桿菌簡介 16
2.3.2 生長曲線 (Growth curve) 16
2.3.3 光催化滅菌機制 18
第三章 文獻回顧 20
3.1 二氧化鈦發展概述 21
3.2 二氧化鈦腐蝕防制 25
3.3 光誘發二氧化鈦表面親水性 28
3.4 二氧化鈦表面抗菌性 39
3.5 溶膠凝膠法 48
3.6 碳鋼於高溫環境之氧化情形 49
第四章 實驗方法 54
4.1實驗方法與流程 54
4.2試片製備 55
4.2.1 試片研磨 55
4.2.2 預長氧化膜 55
4.2.3二氧化鈦薄膜製備 57
4.2.4 製備鑲埋試片 58
4.3電化學分析 58
4.3.1開路電位 (Open Circuit Potential) 59
4.3.2動態極化掃描 (Potential Dynamic Polarization) 59
4.4試片分析 60
4.4.1共軛聚焦微拉曼光譜儀 60
4.4.2低掠角X光繞射 60
4.4.3高解析場發射掃描式電子顯微鏡 61
4.5 接觸角分析 61
4.6 抑菌性分析 61
4.6.1液態培養 62
4.6.2 固態培養 63
4.6.3 生長曲線 65
4.6.4存活曲線 65
第五章 結果與討論 70
5.1 二氧化鈦防蝕特性 70
5.1.1 ITO被覆二氧化鈦 70
5.1.2不同預長氧化膜條件的特性分析 71
5.1.2.1 預長氧化膜拉曼分析 71
5.1.2.2 掃描式電子顯微鏡截面分析 73
5.1.2.3 電化學分析 76
5..1.3 二氧化鈦被覆於不同氧化層的影響 82
5.1.3.1 電化學分析 82
5.1.3.2 SEM截面分析 86
5.1.4 不同二氧化鈦熱處理製程參數的影響 91
5.1.4.1 電化學分析 91
5.1.4.2 SEM截面分析 94
5.1.5 改變紫外光照射強度之電位變化 97
5.2二氧化鈦光誘發表面親水性 99
5.2.1 預長氧化膜碳鋼接觸角 99
5.2.2 二氧化鈦被覆誘發表面親水性 99
5.3 二氧化鈦抗菌性 100
5.3.1 E.Coli 生長曲線 100
5.3.2 紫外光照射時間對E.coli存活之影響 102
5.3.3 不同紫外光強度對E.coli存活之影響 103
第六章 結論 105
第七章 未來工作 107
參考文獻 108

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