博碩士論文 93342006 詳細資訊




以作者查詢圖書館館藏 以作者查詢臺灣博碩士 以作者查詢全國書目 勘誤回報 、線上人數:31 、訪客IP:3.136.25.249
姓名 王韡蒨(Wei-Chien Wang)  查詢紙本館藏   畢業系所 土木工程學系
論文名稱 單維電化學傳輸陽離子技術抑制混凝土ASR之研究
(A Study of Using One Dimension Electrochemical Cation Migration Technique to Inhibit Concrete ASR)
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摘要(中) 加速鋰離子傳輸技術(ALMT)抑制混凝土ASR問題的策略,是利用電場趨動力,在移除會誘發混凝土ASR問題的Na+及K+同時,送入可以抑制ASR問題的Li+。本研究先探討電場條件、試體材料配比及ASR劣化程度差異等,對ALMT試驗的陽離子傳輸行為影響,從中尋找評估陽離子傳輸參數的指標,並提出需要獲得的陽離子傳輸參數項目及分析方法,建立陽離子傳輸參數與傳輸指標之間的關係。結果顯示,陰極槽內的陽離子濃度-時間曲線,依ASR劣化程度區分為二種類型,而二者相同處,是均包含Na+及K+穩定移出及移出完成二個傳輸階段,而Li+均可區分為非穩態、過渡及穩態三個傳輸階段。二者相異處,是ASR劣化程度較高者,Li+達到穩態階段所需時間較短。藉分析陰極槽內的陽離子濃度-時間曲線,可以獲得Na+及K+移出完成時間、移出量及單位時間移出量、Li+穿過試體時間、非穩態傳輸係數、穩態流量及穩態傳輸係數等參數,縱使試驗條件改變,上述參數與適合作為傳輸指標的電流密度之間,都可以建立適當的趨勢關係。增加電場強度、縮短試體長度、增加粒料體積比例、減少水泥含鹼量、增加水灰比及增加試體ASR劣化程度,均可增加Na+及K+的單位時間移出量,縮短Na+及K+移出完成時間,縮短Li+穿過試體時間,增加Li+穩態流量及傳輸係數。
由傳輸進入陰極槽內的陽離子累積帶電量與施加電量曲線,發現可以Na+移出完成時的累積施加電量為界,區分為Na+及K+穩定移出及Li+穩態傳輸二個線性段,二者斜率(TA及TLi)分別代表施加電量用於陽離子傳輸的比例,可以發現TA均大於TLi。增加電場強度、縮短試體長度、增加粒料體積比例、增加試體水灰比、試體ASR劣化程度增加等,均會提高TA及TLi值。增加系統含鹼量則會提高TA值,但會降低TLi值。
最後,本研究以如何獲得欲抑制ASR問題混凝土在電場作用下的Li+、Na+及K+傳輸參數,所需要進行的試驗程序、觀察項目、可套用的理論分析式,及傳輸參數與電流密度關係式特性等,建構一個容易遵循的標準化分析程序,可以提供工程實務運用單維電場抑制混凝土ASR時,作為獲得設計參數的方法。
摘要(英) The Accelerated Migration Technique (ALMT) uses the driving force of electrical field to remove Na+ and K+ from concrete, and simultaneously drive Li+ into concrete to inhibit alkali-silica reaction (ASR). This study discusses the behavior of cations under ALMT influencing by the electrical field conditions, the proportion of concrete mixtures, and the ASR deterioration degree, firstly, to seek the evaluated index of the migration parameters of cations, propose the required items of the parameter and the analysis method, then establish the relationship between the migration parameters and the index. The result shows that the curves between the cation concentrations in catholyte and time, can be divided into two types according to the ASR deterioration degree of concrete. The two types both contain the Na+ and K+ stable migration and the completed migration stages, and the Li+ non-steady state, transition, and steady state. For concrete with higher ASR deterioration degree, the needed time to reach the Li+ steady state is shorter. From the curve between the cation concentrations in catholyte and time, the required migration parameters can be obtained, including the removal time, removal amount and unit time removal amount of the Na+ and K+, and the passing time, the non-steady state migration coefficient, the steady state flux and migration coefficient of the Li+. Though the test condition may change, the above parameters can still establish suitable relationship with the applied current density. Increasing the electrical field, a/c ratio, w/c ratio and the ASR deterioration degree, and reducing the length of sample and alkali amount of cement, can increase the unit time removal amount and reduce the removal time of the Na+ and K+, reduce passing time and increase the steady flux and migration coefficient of the Li+.
The relationship between the cations accumulated charge migrating into the catholyte and the applied charge shows that the curve include the alkalis removed and the Li+ impregnated linear regions (TA and TLi). The accumulated charge until Na+ is removed completely is found just in the boundary between the two regions. The linear slope of the alkalis removed region is greater. While increasing the applied voltage, a/c ratio, w/c ratio, and the ASR deterioration degree, and decreasing the length of sample, can increase the proportion of the applied charge being used for cation migration. But increasing the system alkali amount can increase TA and reduce TLi.
Finally, this research proposes the standardized procedure to obtained the migration parameters of the Li+, Na+, and K+, including the needed testing steps, the observing items, may applied theory, and the relationship between the migration parameters and the current density.
關鍵字(中) ★ 混凝土
★ 砂漿
★ 傳輸
★ 鹼-矽反應
★ 電化學
關鍵字(英) ★ Mortar
★ Concrete
★ Migration
★ Electrochemical
★ Alkali-silica reaction
論文目次 中文摘要 i
Abstract iii
誌謝 v
符號對照表 ix
目錄 xiii
圖目錄 xx
表目錄 xxxv
第一章 緒論 1
1.1  研究起源與動機 1
1.2  研究目的 2
1.3  研究內容 3
第二章 文獻回顧 5
2.1  鹼質與粒料反應 5
2.2  ASR的影響因素 8
2.3  預防及抑制ASR的方法 16
2.4  Li化合物用於抑制ASR的研究 17
2.5  電化學技術評估混凝土耐久性研究現況 24
2.6  ALMT抑制ASR的策略及通電模組 30
2.7  ALMT運用時與ASR有關陽離子的傳輸模式 30
2.8  ALMT通電過程Li+非穩態及穩態階段的傳輸係數計算方法 31
2.9  影響ALMT試驗離子傳輸行為的因素 34
2.10 ALMT實務應用可能面臨的問題分析 36
2.11 ALMT對鋼筋混凝土性質影響 37
2.12 以防水策略抑制混凝土ASR的案例介紹 38
2.13 含Li溶液以浸泡或加壓方式抑制混凝土ASR的案例介紹 38
2.14 電化學技術抑制混凝土ASR的案例介紹 39
第三章 研究方法 41
3.1  研究流程 41
3.2  試驗編號 47
3.3  試驗材料 51
3.3.1 粒料 51
3.3.2 水 51
3.3.3 水泥 52
3.3.4 化學藥劑 53
3.4  試驗方法及步驟 54
3.4.1 加速鋰離子傳輸技術(ALMT) 54
3.4.1.1 通電模組 54
3.4.1.2 配合設計及含鹼量調整 56
3.4.1.3 ALMT試體製作及養護 57
3.4.1.4 ALMT試體之選取 58
3.4.1.5 ALMT試體通電前處理 58
3.4.1.6 電解槽溶液配置 60
3.4.1.7 通電處理後試體內部離子含量分析 60
3.4.1.8 離子層析儀試驗步驟 63
3.4.2 試體經通電處理後的成效驗證 64
3.4.2.1 膨脹量量測 64
3.4.2.2 抗壓強度試驗 64
3.4.2.3 X光繞射試驗(XRD) 64
3.5  試驗主要設備及器材 65
3.5.1 粒料處理及試體製作設備 65
3.5.2 ALMT通電模組 66
3.5.3 超純水機 67
3.5.4 離子層析儀(IC) 69
3.5.5 ALMT試驗的試體前處理系統 70
3.5.6 研磨機及切割機 70
3.5.7 膨脹量量測模組 71
3.5.8 水溶法試驗相關設備組 73
3.5.9 其它 74
第四章 ALMT通電技術的陽離子傳輸行為及抑制ASR成效分析 75
4.1  試驗目的 75
4.2  試驗作法 75
4.3  陰極槽內電解液溫度與電壓的歷時變化 76
4.4  陰極槽內的陽離子濃度與電壓歷時變化 77
4.5  試體內游離態Li+、Na+及K+分佈的歷時變化 85
4.6  ALMT抑制砂漿ASR問題所需的鹼質移出量與Li+送入量分析 89
4.7  利用試體內Li+含量分佈計算Li+的非穩態傳輸係數 91
4.8  累積施加電量與離子累積帶電量關係 100
4.9  小結 104
第五章 施加定電壓的ALMT對陽離子在砂漿內傳輸行為的影響 107
5.1  試驗目的 107
5.2  試驗作法 107
5.3  溫度、電流及系統阻抗的歷時變化 108
5.4  陰極槽內的陽離子濃度與電流的歷時變化 111
5.5  通電後試體內游離態Li+、Na+及K+分佈 120
5.6  累積施加電量與離子累積帶電量關係 122
5.7  小結 126
第六章 施加定電流密度的ALMT對陽離子在砂漿內傳輸行為的影響 127
6.1  試驗目的 127
6.2  試驗作法 127
6.3  溫度、電壓及系統阻抗的歷時變化 128
6.4  陰極槽內的陽離子濃度與電壓歷時變化 134
6.5  通電後試體內游離態Li+、Na+及K+分佈 141
6.6  累積施加電量與離子累積帶電量關係 142
6.7  小結 148
第七章 以施加電流密度作為ALMT評估陽離子傳輸行為指標的可行性 151
7.1  試驗目的 151
7.2  試驗作法 151
7.3  陰極槽內的陽離子濃度與電流的歷時變化 151
7.4  初始電壓與電流關係 153
7.5  系統阻抗的歷時變化 154
7.6  試驗全程平均溫度與電流密度關係 155
7.7  Na+及K+的移出 156
7.8  Li+的送入 164
7.9  陽離子的遷移數 169
7.10 小結 172
第八章 試體長度對不同施加定電流密度的ALMT陽離子傳輸行為影響 173
8.1  試驗目的 173
8.2  試驗作法 173
8.3  試驗溫度、電壓及系統阻抗比較 174
8.4  陰極槽內的陽離子濃度與電壓的歷時變化 179
8.5  累積施加電量與離子累積帶電量關係 193
8.6  小結 197
第九章 粒料水泥比例對ALMT的陽離子傳輸行為影響 199
9.1  試驗目的 199
9.2  試驗作法 199
9.3  溫度、電壓及系統阻抗 200
9.4  陰極槽內的陽離子濃度與電壓的歷時變化 204
9.5  累積施加電量與離子累積帶電量關係 224
9.6  粒料對Li+傳輸係數的影響 230
9.7  小結 233
第十章 水泥含鹼量對ALMT的陽離子傳輸行為影響 235
10.1 試驗目的 235
10.2 試驗作法 235
10.3 溫度、電壓及系統阻抗 237
10.4 陰極槽內的陽離子濃度與電壓的歷時變化 245
10.5 累積施加電量與離子累積帶電量關係 266
10.6 小結 272
第十一章 水灰比對ALMT的陽離子傳輸行為影響 275
11.1 試驗目的 275
11.2 試驗作法 275
11.3 溫度、電壓及系統阻抗 277
11.4 陰極槽內的陽離子濃度與電壓的歷時變化 283
11.5 累積施加電量與離子累積帶電量關係 299
11.6 小結 305
第十二章 ALMT運用於已產生ASR劣化試體時的陽離子傳輸行為影響 307
12.1 試驗目的 307
12.2 試驗作法 307
12.3 溫度、電壓及系統阻抗的歷時變化 308
12.4 陰極槽內的陽離子濃度與電壓的歷時變化 315
12.5 通電後試體內游離態Li+、Na+及K+分佈 328
12.6 累積施加電量與離子累積帶電量關係 332
12.7 小結 336
第十三章 ALMT應用時的有效電極間距分析 339
13.1 試驗目的 339
13.2 試驗作法 339
13.3 溫度、電壓及系統阻抗的歷時變化 340
13.4 陰極槽內的陽離子濃度與電壓的歷時變化 344
13.5 通電後試體內游離態Li+、Na+及K+分佈 357
13.6 通電對混凝土抗壓強度影響 364
13.7 小結 366
第十四章 獲得單維ALMT實務應用所需參數的分析程序建議 369
14.1 現有電化學技術在進行抑制混凝土ASR問題時所面臨的問題 369
14.2 「加速鋰離子傳輸技術」抑制混凝土ASR問題的想法 369
14.3 獲得單維ALMT實務應用所需參數的分析程序建議 371
14.4 「獲得單維ALMT實務應用所需參數的分析程序」在實務上之應用建議 379
第十五章 結論與建議 381
15.1 結論 381
15.2 建議 385
參考文獻 387
圖目錄
圖2.1  含鹼量對於混凝土角柱膨脹量影響(環境溫度控制在38 °C) 11
圖2.2  ASR活性粒料在高OH-濃度環境的溶解量 12
圖2.3  儲存環境的相對濕度對混凝土角柱膨脹量影響 13
圖2.4  ALMT試驗配置示意圖 30
圖2.5  典型的ALMT試驗陰極槽內陽離子濃度與電壓-時間曲線 31
圖2.6  陰極槽內Li+濃度變化 33
圖3.1  主研究流程圖 43
圖3.2  研究流程圖A-D 44
圖3.3  研究流程圖E 45
圖3.4  研究流程圖F 46
圖3.5  ALMT模組示意圖 55
圖3.6  數據擷取器監測電流與電壓之配線圖 55
圖3.7  ALMT試體選取示意圖 58
圖3.8  試體加封步驟及使用器材(以高度5cm為例) 59
圖3.9  進行試體內部離子含量分析前試體切割方式 61
圖3.10 水溶法試驗流程 62
圖3.11 粒料處理及試體製作設備 65
圖3.12 壓克力槽與電極材料 66
圖3.13 溫度量測儀器 66
圖3.14 ALMT通電模組及資料擷取設備 67
圖3.15 超純水機配置示意圖 67
圖3.16 離子層析儀、自動進樣器及電腦軟體設備 69
圖3.17 ALMT試驗的試體前處理設備 70
圖3.18 研磨機及內部構造 71
圖3.19 切割機 71
圖3.20 膨脹量量測試驗模組及測點黏貼儀示意圖 72
圖3.21 膨脹量量測設備 73
圖3.22 水溶法試驗所需相關儀器 74
圖4.1  通電1440小時的ALMT試驗陰極槽電解液溫度與電壓歷時曲線 76
圖4.2  ALMT試驗過程中陰極槽內的陽離子濃度與電壓歷時曲線 77
圖4.3  ALMT試驗求取Na+及K+完成移出試體所需時間的作法 79
圖4.4  Na+及K+移出百分比的歷時變化 80
圖4.5  陽極槽電解液內的Li+濃度-時間曲線 81
圖4.6  陽極槽電解液內的Li+送入試體量-時間曲線 82
圖4.7  陰極槽電解液內的Li+濃度-時間曲線迴歸分析 83
圖4.8  陰極槽內Li+濃度-時間曲線的穩態傳輸階段線性迴歸分析 85
圖4.9  試體內游離態Na+含量的歷時變化 86
圖4.10 試體內游離態K+含量的歷時變化 87
圖4.11 試體內游離態Na2Oeq的歷時變化 87
圖4.12 試體內游離態Li+含量的歷時變化 88
圖4.13 試體內游離態Li/(Na+K)莫耳比的歷時變化 89
圖4.14 經不同通電歷時處理試體置於38 °C 100 % R.H加速劣化環境的膨脹量 90
圖4.15 理論的濃度輪廓 93
圖4.16 ALMT通電4、8、32、60及120小時試體內Li+含量 94
圖4.17 ALMT通電180、240、360、420及480小時試體內Li+含量 94
圖4.18 ALMT通電540、720、960、1200及1440小時試體內Li+含量 95
圖4.19 ALMT試驗0-180小時的陰極槽Li+濃度曲線 95
圖4.20 通電0 – 180小時的Dnf與時間關係曲線 97
圖4.21 ALMT試驗過程累積施加電量與離子累積帶電量關係 100
圖4.22 累積施加電量與Na+及K+穩定移出及Li+穩態傳輸階段的累積帶電量關係 102
圖4.23 累積施加電量與陽離子累積帶電量關係 103
圖5.1  ALMT試驗陰極槽電解液的平均溫度與施加電壓關係 108
圖5.2  ALMT試驗陰極槽電解液的平均溫度(T)與通電全程的平均電流密度(i)關係 109
圖5.3  ALMT通電歷時的電流變化 110
圖5.4  典型試驗的溫度與電流歷時曲線(以V30為例) 110
圖5.5  ALMT通電歷時的系統阻抗變化 111
圖5.6  典型的定電壓ALMT試驗過程陰極槽電解液內陽離子濃度與施加電流的歷時曲線(以V30為例) 112
圖5.7  Na+及K+單位時間平均移出量與施加電壓關係 114
圖5.8  Na+及K+單位時間平均移出量與Na+及K+移出完成前的平均施加電流密度關係 115
圖5.9  Li+穿過試體時間t0.1與(a)施加電壓及(b)非穩態階段平均施加電流密度關係 117
圖5.10 Li+穩態流量及傳輸係數與(a)施加定電壓(b)及平均電流密度的關係 119
圖5.11 Li+的穩態流量(Js)與穩態傳輸係數(Ds)關係 120
圖5.12 通電後試體內游離態陽離子含量 121
圖5.13 傳輸進入陰極槽內的陽離子帶電量與累積施加電量的關係 122
圖5.14 典型的陰極槽內陽離子帶電量與累積施加電量的關係(以V40為例) 124
圖5.15 施加電量用於陽離子傳輸比例與施加電壓的關係 124
圖5.16 施加電量用於陽離子傳輸比例與平均施加電流密度的關係 125
圖6.1  ALMT試驗陰極槽電解液的平均溫度(T)與施加電流密度(i)關係 129
圖6.2  定電流密度ALMT通電歷時的電壓變化 130
圖6.3  定電流密度ALMT試驗的溫度與電壓歷時曲線(以C21為例) 130
圖6.4  定電流密度ALMT通電歷時的系統阻抗變化 131
圖6.5  電壓未大幅上升前的平均電壓(Va)與電流(I)關係 131
圖6.6  通電結束後靠近陰極槽試體表面的白色析晶物 132
圖6.7  通電結束後靠近陰極槽試體表面白色析晶物的XRD檢測結果 133
圖6.8  通電結束後靠近陰極槽試體(取樣厚度1cm)的XRD檢測結果 133
圖6.9  典型的定電流密度ALMT過程中陰極槽內陽離子濃度與電壓的歷時曲線(以C12為例) 134
圖6.10 定電流密度ALMT試驗Na+及K+移出完成時間(tNa及tK)與施加電流密度(i)之關係 136
圖6.11 Na+及K+單位時間平均移出量(vNa及vK)與施加定電流密度(i)關係 137
圖6.12 Li+穿過試體時間(t0.1)與電流密度(i)的關係 138
圖6.13 Li+穩態流量(Js)及傳輸係數(Ds)與施加定電流密度(i)的關係 139
圖6.14 Li+的穩態流量(Js)與穩態傳輸係數(Ds)關係 140
圖6.15 Ds/Dn百分比值與電流密度關係 140
圖6.16 通電後試體內游離態陽離子含量 142
圖6.17 典型的陽離子累積帶電量與時間關係(以C15為例) 144
圖6.18 傳輸至陰極槽的陽離子累積帶電量與累積施加電量關係(以C15為例) 144
圖6.19 傳輸進入陰極槽內的陽離子帶電量與累積施加電量的關係 145
圖6.20  Na+及K+穩定移出階段及LI+穩態傳輸階段的陽離子遷移數總和(TA及TLI)與電流密度(I)的關係 146
圖7.1  典型的定電壓ALMT試驗陰極槽內陽離子濃度與電流的歷時曲線(以V30為例) 152
圖7.2  典型的定電流密度ALMT試驗陰極槽內陽離子濃度與電壓的歷時曲線(以C18為例) 153
圖7.3  定電壓(V系列)與定電流密度(C系列)試驗的初始電壓(Vi)與電流(Ii)關係 154
圖7.4  定電壓(V系列)與定電流密度(C系列)試驗中系統阻抗的歷時變化 155
圖7.5  ALMT試驗陰極槽試驗過程的平均溫度(T)與平均電流密度(i)關係 156
圖7.6  ALMT試驗(a) Na+與(b) K+移出完成時間(tNa及tK)與平均電流密度(i)關係 159
圖7.7  ALMT試驗(a) Na+與(b) K+移出量與平均電流密度關係 160
圖7.8  ALMT試驗Na+與K+移出百分比與平均電流密度關係 161
圖7.9  ALMT試驗Na+與K+單位時間移出量(vNa與vK)與平均電流密度(i)關係 163
圖7.10 Li+穿過試體時間(t0.1)與施加平均電流密度(i)的關係 165
圖7.11 Li+非穩態傳輸係數(Dn)與施加平均電流密度(i)的關係 166
圖7.12 Li+穩態流量(Js)與施加平均電流密度(i)的關係 167
圖7.13 Li+穩態傳輸係數(Ds)與施加平均電流密度(i)的關係 168
圖7.14 Li+穩態傳輸係數(Ds)與穩態流量(Js)的關係 168
圖7.15 Li+的Dn/Ds(%)與施加平均電流密度(i)的關係 169
圖7.16 Na+移出階段的陽離子遷移數總和與電流密度的關係 170
圖7.17 Li+穩態傳輸階段的陽離子遷移數總和與電流密度的關係 171
圖8.1  ALMT試驗陰極槽平均溫度(T3C及TC)與施加電流密度(i)關係 174
圖8.2  ALMT試驗陰極槽平均溫度比值(Tn,3C及Tn,C)與施加電流密度(i)關係 175
圖8.3  定電流密度ALMT通電歷時的電壓變化(a) 3C系列(b) C系列 176
圖8.4  3C系列及C系列的初始電壓(Vi,3C及Vi,C)與施加電流(I)關係 177
圖8.5  定電流密度ALMT通電歷時的系統阻抗變化 178
圖8.6  3C系列及C系列在施加電壓未大幅上升前的平均電壓(VA,3C及VA,C)與施加電流(I)關係 179
圖8.7  典型的定電流密度ALMT過程陰極槽陽離子濃度與電壓的歷時曲線(以(a) 3C12和(b) C12為例) 180
圖8.8  試驗3C系列及C系列的(a)Na+及(b)K+移出完成時間與電流密度關係 183
圖8.9  試驗3C系列及C系列的(a)Na+及(b)K+移出百分比與電流密度關係184
圖8.10 試驗3C系列及C系列的鹼質移出量百分比與電流密度關係 185
圖8.11 試驗3C系列及C系列的(a)Na+及(b)K+單位時間平均移出量(vNa及vK)與施加定電流密度(i)關係 186
圖8.12 試驗3C系列及C系列的Li+穿過試體時間t0.1與電流密度的關係 188
圖8.13 試驗3C系列及C系列的Li+非穩態傳輸係數(Ds)與電流密度的關係188
圖8.14 試驗3C系列及C系列的Li+穩態流量(Js)與電流密度(i)的關係 190
圖8.15 試驗3C系列及C系列的Li+穩態傳輸係數(Ds)與電流密度(i)的關係190
圖8.16 試驗3C系列及C系列的Li+穩態傳輸係數(Ds,3C及Ds,C)與穩態流量 (Js,3C及Js,C)的關係 191
圖8.17 試驗3C系列及C系列的Ds/Dn比值與電流密度關係 192
圖8.18 典型的陽離子累積帶電量與時間關係(以3C15為例) 194
圖8.19 試驗3C系列及C系列的(a) Na+及K+移出階段及(b) Li+穩態傳輸階段的陽離子遷移數總和與電流密度的關係 196
圖9.1  ALMT試驗陰極槽平均溫度(T)與施加電流密度(i)關係 201
圖9.2  ALMT試驗陰極槽平均溫度(T)與粒料體積比例(Vf)關係 202
圖9.3  ALMT試驗(a) 初始電壓(Vi)及(b) 平均電壓(Va)與施加電流密度(i)關係 203
圖9.4  初始及平均系統阻抗(RI及RA)與粒料體積比例(VF)關係 204
圖9.5  典型的試驗過程陰極槽陽離子濃度與電壓的歷時曲線(以LA9為例) 205
圖9.6  典型的試驗過程陰極槽陽離子濃度與電壓的歷時曲線(以MA9為例)
206
圖9.7  典型的試驗過程陰極槽陽離子濃度與電壓的歷時曲線(以HA9為例) 206
圖9.8  LA、MA及HA系列試驗(A) NA+及(B) K+移出完成時間(TNA及TK)與電流密度(I)關係 208
圖9.9  LA、MA及HA系列試驗(A) NA+及(B) K+移出完成時間(TNA及TK)與粒料體積比例(VF)關係 210
圖9.10 LA、MA及HA系列試驗(A) NA+及(B) K+單位時間移出量(VNA及VK)與施加定電流密度(I)關係 212
圖9.11 LA、MA及HA系列試驗(A) NA+及(B) K+單位時間移出量(VNA及VK)與粒料體積比例(VF)關係 214
圖9.12 LA、MA及HA系列試驗LI+穿過試體時間(T0.1)與電流密度(I)關係 216
圖9.13 LA、MA及HA系列試驗LI+穿過試體時間(T0.1)與粒料體積比例(VF)關係 217
圖9.14 LA、MA及HA系列試驗LI+的DN值與電流密度關係 217
圖9.15 LA、MA及HA系列試驗LI+的DN值與粒料體積比例關係 218
圖9.16 LA、MA及HA系列試驗LI+穩態流量(JS)與施加定電流密度(I) 關係 219
圖9.17 LA、MA及HA系列試驗LI+穩態傳輸係數(DS)與施加定電流密度(I)關係 220
圖9.18 LA、MA及HA系列試驗LI+穩態流量(JS)與粒料體積比例(VF)關係 221
圖9.19 LA、MA及HA系列試驗LI+穩態傳輸係數(DS)與粒料體積比例(VF)關係 222
圖9.20 LA、MA及HA系列試驗LI+的穩態流量(JS)與穩態傳輸係數(DS)關係 222
圖9.21 LA、MA及HA系列試驗DS/DN百分比值與電流密度關係 223
圖9.22 LA、MA及HA系列試驗DS/DN百分比值與粒料體積比例關係 224
圖9.23典型的陰極槽內陽離子累積帶電量與累積施加電量關係(以LA9為例) 225
圖9.24 LA、MA及HA系列試驗NA+及K+穩定移出階段的陽離子遷移數總和(TA)與電流密度的關係 227
圖9.25 LA、MA及HA系列試驗LI+穩態傳輸階段的陽離子遷移數總和(TLI)與電流密度的關係 228
圖9.26 LA、MA及HA系列試驗NA+及K+穩定移出階段的陽離子遷移數總和(TA)與粒料體積比例(VF)關係 229
圖9.27 LA、MA及HA系列試驗LI+穩態傳輸階段的陽離子遷移數總和(TLI)與粒料體積比例(VF)關係 230
圖9.28 以(Vf=0.46的Ds)為基準正規化的Li+傳輸係數與粒料體積比例理論及試驗結果關係 232
圖10.1 5N、10N及20N試驗陰極槽平均溫度(T)與施加電流密度(I)關係 237
圖10.2 5N、10N及20N試驗陰極槽平均溫度與水泥含鹼量關係 238
圖10.3 5N、10N及20N試驗(A) 初始電壓(VI)及(B) 平均電壓(VA)與施加電流密度(I)關係 239
圖10.4 5N、10N及20N系列試驗(A) 初始電壓(VI)及(B) 平均電壓(VA)與水泥含鹼量(CA)關係 241
圖10.5 5N、10N及20N系列試驗(A) 初始系統阻抗及(B) 平均系統阻抗與水泥含鹼量關係 243
圖10.6 5N、10N及20N系列試驗(A)初始系統阻抗及(B)平均系統阻抗與電流密度關係 244
圖10.7 低含鹼量試體典型的試驗過程陰極槽內陽離子濃度與電壓的歷時曲線(以5N9為例) 246
圖10.8 中等含鹼量試體典型的試驗過程陰極槽陽離子濃度與電壓的歷時曲線(以10N9為例) 246
圖10.9 高含鹼量試體典型的試驗過程陰極槽陽離子濃度與電壓的歷時曲線(以20N9為例) 247
圖10.10 5N、10N及20N系列試驗(a)Na+及(b)K+移出完成時間與電流密度關係 249
圖10.11 5N、10N及20N系列試驗(a)Na+及(b)K+移出完成時間(tNa及tK)與水泥含鹼量關係 251
圖10.12 5N、10N及20N系列試驗(a) Na+及(b) K+移出速率(vNa及vK)與施加定電流密度(i)關係 253
圖10.13 5N、10N及20N系列試驗(a)Na+及(b)K+單位時間移出量(vNa及vK)與水泥含鹼量關係 256
圖10.14 5N、10N及20N系列試驗Li+穿過試體時間(t0.1)與電流密度(i)關係 258
圖10.15 5N、10N及20N系列試驗Li+穿過試體時間(t0.1)與水泥含鹼量 (CA) 關係 259
圖10.16 10N及20N系列試驗Li+的Dn值與電流密度關係 259
圖10.17 5N、10N及20N系列試驗Li+的Dn值與水泥含鹼量關係 260
圖10.18 5N、10N及20N系列試驗Li+穩態流量(Js)與施加定電流密度(i)的關係 261
圖10.19 5N、10N及20N系列試驗Li+穩態傳輸係數(Ds)與施加定電流密度(i)關係 262
圖10.20 5N、10N及20N系列試驗Li+穩態流量與水泥含鹼量關係 263
圖10.21 5N、10N及20N系列試驗Li+穩態傳輸係數(Ds)與水泥含鹼量關係 263
圖10.22 5N、10N及20N系列試驗Li+的穩態流量(Js)與穩態傳輸係數(Ds)關係 264
圖10.23 5N、10N及20N系列試驗砂漿圓柱試體(Ψ10 cm高20 cm)抗壓強度與水泥含鹼量關係 264
圖10.24 5N、10N及20N系列試驗Ds/Dn比值與電流密度關係 265
圖10.25 5N、10N及20N系列試驗Ds/Dn比值與水泥含鹼量關係 266
圖10.26 5N、10N及20N系列試驗典型的陰極槽內陽離子累積帶電量與累積施加電量關係(以10N9為例) 267
圖10.27 5N、10N及20N系列試驗Na+及K+移出階段的陽離子遷移數總和(TA)與電流密度(i)關係 269
圖10.28 5N、10N及20N系列試驗Li+穩態傳輸階段的陽離子遷移數總和(TLi)與電流密度(i)關係 270
圖10.29 5N、10N及20N系列試驗Na+及K+移出階段的陽離子遷移數總和(TA)與水泥含鹼量的關係 271
圖10.30 5N、10N及20N系列試驗Li+穩態傳輸階段的陽離子遷移數總和(TLi)與水泥含鹼量的關係 271
圖11.1 抗壓強度與水灰比關係 276
圖11.2 ALMT試驗陰極槽平均溫度(T)與施加電流密度(i)關係 277
圖11.3 ALMT試驗陰極槽平均溫度(T)與水灰比關係 277
圖11.4 ALMT試驗(a)初始電壓(Vi)及(b)平均電壓(Va)與施加電流密度(i)關係278
圖11.5 ALMT試驗(a)初始電壓(Vi)及(b) 平均電壓(Va)與水灰比關係 280
圖11.6 ALMT試驗(a)初始系統阻抗(Ri)及(b)平均系統阻抗(Ra)與水灰比關係 281
圖11.7 ALMT試驗(a)初始系統阻抗(Ri)及(b)平均系統阻抗(Ra)與電流密度(i)關係 282
圖11.8 典型的試驗過程陰極槽陽離子濃度與電壓的歷時曲線(以4W9為例) 283
圖11.9 典型的試驗過程陰極槽陽離子濃度與電壓的歷時曲線(以5W9為例) 284
圖11.10 典型的試驗過程陰極槽陽離子濃度與電壓的歷時曲線(以6W9為例) 284
圖11.11 ALMT試驗(a) Na+及(b) K+移出完成時間(tNa及tK)與電流密度(i)關係286
圖11.12 ALMT試驗(a) Na+及(b) K+移出完成時間(tNa及tK)與水灰比關係 288
圖11.13 ALMT試驗(a) Na+及(b) K+單位時間移出量(vNa及vK)與施加定電流密度(i)關係 289
圖11.14 ALMT試驗(a)Na+及(b)K+單位時間移出量(vNa及vK)與水灰比關係 291
圖11.15 ALMT試驗Li+穿過試體時間(t0.1)與電流密度關係 293
圖11.16 ALMT試驗Li+穿過試體時間(t0.1)與水灰比關係 293
圖11.17 ALMT試驗Li+的Dn值與電流密度關係 294
圖11.18 ALMT試驗Li+的Dn值與水灰比關係 294
圖11.19 Li+穩態流量(Js)與施加定電流密度(i)的關係 295
圖11.20 Li+穩態傳輸係數(Ds)與施加定電流密度(i)的關係 295
圖11.21 Li+穩態流量(Js)與水灰比的關係 296
圖11.22 Li+穩態傳輸係數(Ds)與水灰比的關係 297
圖11.23 Li+的穩態流量(Js)與穩態傳輸係數(Ds)關係 297
圖11.24 Ds/Dn比值與電流密度關係 298
圖11.25 Ds/Dn比值與水灰比關係 299
圖11.26 典型的陰極槽內陽離子累積帶電量與累積施加電量關係(以6W9為例) 300
圖11.27 Na+及K+移出階段的陽離子遷移數總和(TA)與電流密度的關係 302
圖11.28 Li+穩態傳輸階段的陽離子遷移數總和(TLi)與電流密度的關係 302
圖11.29 Na+及K+移出階段的陽離子遷移數總和(TA)與水灰比的關係 304
圖11.30 Li+穩態傳輸階段的陽離子遷移數總和(TLi)與水灰比的關係 304
圖12. 1 AE及NC系列試驗陰極槽平均溫度(T)與施加電流密度(i)關係 309
圖12. 2 NC系列通電歷時的電壓變化 310
圖12. 3 AE系列通電歷時的電壓變化 310
圖12. 4 AE及NC系列(a)初始電壓(Vi)及(b)平均電壓(Va)與施加電流密度(i)關係 310
圖12. 5 溫度與電壓的歷時曲線(以NC9為例) 313
圖12. 6 溫度與電壓的歷時曲線(以AE9為例) 314
圖12. 7 AE及NC系列(a) 初始系統阻抗(Ri)及(b) 平均系統阻抗(Ra)與電流密度(i)關係 315
圖12. 8 典型的定電流密度ALMT過程陰極槽陽離子濃度與電壓的歷時曲線(以(a) NC15及(b) AE15為例) 316
圖12. 9 小型砂漿圓柱試體(Ψ1 cm ? 5 cm)在38 °C、100 %環境一年的膨脹量318
圖12.10 AE及NC系列(a) Na+及(b) K+移出完成時間(tNa及tK)與電流密度(i)關係 320
圖12.11 AE及NC系列(a)Na+及(b)K+單位時間平均移出量(vNa及vK)與施加定電流密度(i)關係 322
圖12.12 AE及NC系列試驗Li+穿過試體時間t0.1與電流密度的關係 324
圖12.13 AE及NC系列試驗Li+(a) 穩態流量(Js)及(b) 傳輸係數(Ds)與施加定電流密度(i)的關係 326
圖12.14 AE及NC系列試驗Li+的穩態傳輸係數(Ds)與穩態流量(Js)關係 327
圖12.15 AE及NC系試驗列的Ds/Dn比值與電流密度關係 328
圖12.16 NC系列通電試驗後試體內游離態陽離子含量 329
圖12.17 AE系列通電試驗後試體內游離態陽離子含量 330
圖12.18 AE及NC系列通電試驗後試體內游離態Li+含量 331
圖12.19 AE及NC系列通電試驗後試體內游離態Li/(Na+K)莫耳比與累積施加電量(QA)關係 332
圖12.20 典型的陰極槽內陽離子累積帶電量與累積施加電量關係(以AE15為例) 333
圖12.21 AE及NC系列試驗Na+及K+移出階段的陽離子遷移數總和(TA)與電流密度的關係 335
圖12.22 AE及NC系列試驗Li+穩態傳輸階段的陽離子遷移數總和(TLi)與電流密度的關係 335
圖13.1 通電過程的溫度與室溫歷時變化(以L5C為例) 341
圖13.2 試驗L5C、L7C及L9C通電歷時的電壓變化 342
圖13.3 試驗L11V、L14V、L17V、L20V及L23V通電歷時的電流變化 342
圖13.4 通電歷時的系統阻抗變化 344
圖13.5 典型的定電流密度ALMT試驗過程陰極槽陽離子濃度與電壓的歷時曲線(以L9C為例) 346
圖13.6 典型的定電壓ALMT試驗過程陰極槽陽離子濃度與電流的歷時曲線(以L17V為例) 347
圖13.7 典型的定電流密度ALMT試驗過程陰極槽陽離子濃度與電壓的累積施加電量曲線(以L9C為例) 348
圖13.8 典型的定電壓ALMT試驗過程陰極槽陽離子濃度與電流的累積施加電量曲線(以L17V為例) 348
圖13.9 電極間距(L)與NA+及K+穩定移出階段的單位施加電量移出量 (RMNa及RMK)的關係 350
圖13.10 NA+及K+穩定移出階段的平均電流(I)與單位施加電量移出鹼量(RMNa及RMK)關係 351
圖13.11 電極間距與鹼質移出量百分比關係 352
圖13.12 鹼質移出階段的鹼質移出量與平均施加電流關係 352
圖13.13 Li+非穩態階段平均電流與電極間距關係 354
圖13.14 達t0.1時所需要的累積施加電量(Q0.1)與電極間距(L)關係 355
圖13.15 達t0.1時的所需時間與電極間距(L)關係 355
圖13.16 Li+的非穩態傳輸係數Dn與電極間距(L)關係 356
圖13.17 Li+穩態傳輸係數(Ds)與電極間距(L)關係 357
圖13.18 不同電極間距試驗通電後試體內游離態Li+含量 358
圖13.19 不同電極間距試驗通電後試體內游離態Na+含量 358
圖13.20 不同電極間距試驗通電後試體內游離態K+含量 359
圖13.21 不同電極間距試驗通電後試體內游離態Li/(Na+K)含量莫耳比分佈圖 363
圖13.22 不同電極間距試驗通電後試體內游離態Li/(Na+K)含量莫耳比取1.0以下區域觀察 363
圖13.23 通電試體抗壓強度增加百分比(ΔFC,%)與試體長度(L)關係 365
圖13.24 通電組及未通電控制組的抗壓強度(FC,E及FC,C)與試體長度(L)關係 365
圖14.1 二維的電場作用的電場線分佈示意圖 370
圖14.2 修正的ALMT試驗模組 372
圖14.3 典型劣化程度尚低混凝土的ALMT試驗離子濃度–時間曲線(以C12為例) 373
圖14.4 典型劣化程度較高混凝土的ALMT試驗離子濃度–時間曲線(以AE15為例) 374
圖14.5 陰極槽電解液內的LI+濃度-時間曲線過渡階段的迴歸分析 376
圖14.6 陰極槽內LI+濃度-時間曲線的穩態傳輸階段線性迴歸分析 377
表目錄
表2.1  易產生ASR的岩石種類及所含的相關礦物 9
表2.2  主要的含鋰礦物化學組成及產地 17
表2.3  相關研究所發現有效的Li化合物劑量 22
表2.4  總電流量與氯離子滲透性關係 25
表2.5  電滲方法之發展 29
表3.1  試驗試體編號一覽表 47
表3.2  東河馬武窟溪變質砂岩的ASR粒料活性檢測結果 51
表3.3  東河變質砂岩的岩相分析結果 51
表3.4  水泥化學成分 52
表3.5  水泥物理性質 53
表3.6  試驗藥品資訊 53
表3.7  流洗液及標準液藥品資訊 54
表3.8  ASTM C227細粒料級配分佈 56
表3.9  超純水機設備規格 68
表4.1  依式(4.6)計算Li+的傳輸係數Dnf 96
表4.2  依式(4.12)計算Li+的傳輸係數Deff 99
表5.1  施加定電壓的ALMT試驗編號及通電條件 108
表5.2  由陰極槽電解液內的Na+及K+濃度-時間曲線所獲得的分析結果 113
表5.3  施加定電壓的ALMT試驗過程不同離子傳輸階段的平均電流密度 115
表5.4  Li+非穩態及穩態傳輸係數 116
表5.5  ALMT試驗後試體內的游離態Li/(Na+K)莫耳比 122
表5.6  Na+移出完成時的累積施加電量 123
表6.1  施加電流密度的ALMT試驗編號及通電條件 128
表6.2  由陰極槽電解液內的Na+及K+濃度-時間曲線所獲得的結果 135
表6.3  Li+非穩態及穩態傳輸係數 137
表6.4  定電流密度ALMT試驗後試體內的游離態Li/(Na+K)莫耳比 142
表6.5  Na+移出完成時的累積施加電量 145
表7.1  由陰極槽電解液內的Na+及K+濃度-時間曲線所獲得的分析結果 157
表7.2  Li+非穩態及穩態傳輸係數 164
表8.1  3C及C系列試驗由陰極槽內的NA+及K+濃度-時間曲線所獲得的結果 187
表8.2  試驗3C系列及C系列Li+非穩態及穩態傳輸係數 187
表8.3  試驗3C系列及C系列的Na+移出完成時的累積施加電量 194
表9.1  試驗配比及施加電場條件 200
表9.2   LA、MA及HA系列試驗陰極槽內的Na+及K+濃度-時間曲線所獲得的結果 207
表9.3  Li+非穩態及穩態傳輸係數 215
表9.4  LA、MA及HA系列試驗陽離子累積帶電量與累積施加電量曲線的
TA及TLI試驗值 226
表9.5  理論的Ds/D0與試驗的Ds/(Vf=0.46的DS,LA))結果 232
表10.1 試驗配比及施加電場條件 236
表10.2 5N、10N及20N系列試驗由陰極槽內的Na+及K+濃度-時間曲線所獲得的結果 248
表10.3 ALMT通電過程Na及K在試體孔隙溶液中的平均解離度比值 257
表10.4 Li+非穩態及穩態傳輸係數 257
表10.5 5N、10N及20N系列陽離子累積帶電量與累積施加電量曲線的TA及TLi試驗值 268
表11.1 試驗配比及施加電場條件 276
表11.2 由陰極槽內的Na+及K+濃度-時間曲線所獲得的結果 285
表11.3 Li+非穩態及穩態傳輸係數 292
表11.4 陽離子累積帶電量與累積施加電量曲線的TA及TLi試驗值 301
表12.1 AE及NC系列試驗陰極槽內的Na+及K+濃度-時間曲線所獲得的結果 219
表12.2 Li+非穩態及穩態傳輸係數 323
表12.3 NC系列試驗後試體內的游離態Li/(Na+K)莫耳比 329
表12.4 AE系列試驗後試體內的游離態Li/(Na+K)莫耳比 330
表12.5 陽離子累積帶電量與累積施加電量曲線的TA及TLi試驗值 334
表13.1 混凝土配比設計各材料所需用量 339
表13.2 試驗編號及通電條件 340
表13.3 通電過程的平均電解液溫度及室溫一覽表 341
表13.4 試驗編號及通電條件 343
表13.5 由陰極槽內的Na+及K+濃度-累積施加電量曲線所獲得的結果 349
表13.6 Li+非穩態及穩態傳輸係數 353
表13.7 通電後試體內的游離態Na2Oeq分佈 361
表13.8 通電組與未通電控制組混凝土的抗壓強度一覽表 364
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指導教授 李釗(Chau Lee) 審核日期 2010-6-28
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