臺灣博碩士論文加值系統

　　泥岩本身含有溶解鹽類導致其鈉交換比(ESP)高，泥岩遇水後產生回脹崩解行為，簡言之，泥岩具有遇水敏感（Watersensitive）特性，此外泥岩中特定溶出鹽類是否改變其地工性質亟待進一步釐清。為能有效探討溶出參數對夯實泥岩襯裡回脹及滲透行為之影響，本實驗使用萃取、離心、過濾、濃縮及結晶等固液分離技術獲得特定溶出鹽類後，以掃描式電子顯微鏡及元素分析(SEM/EDX)及X光繞射分析(XRF/XRD)進行鑑定，進一步以環境掃描式電子顯微鏡及元素分析(ESEM/EDX)觀察泥岩浸水時固相之顯微結構及元素成份變化，以溶出參數分析觀察泥岩浸水時液相之水質變化，此外採用夯實及滲透實驗求得夯實泥岩襯裡施工鋪設之可接受區(Acceptable zone)，基於可接受區製備自由回脹、受限回脹滲透實驗的標準試體進行試驗，並同步量測溶出參數分析(包括導電度、酸鹼值及離子分析)，最後建立溶出參數與夯實泥岩襯裡自由回脹、受限回脹及滲透行為之關係。
　　基於上述研究分析結果，可歸納以下幾點結論：

1.泥岩及其特定溶出鹽類鑑定
　　經土壤基本物化分析得知泥岩飽和萃取導電度(ECe)>4 m mho cm-1及ESP>15%，由此判定泥岩屬鹽鹼土，此外泥岩浸水後呈現弱鹼性應是Na+離子的水解造成，泥岩特定溶出鹽類經由SEM/EDX及XRF/XRD鑑定後確認為Na2SO4及NaCl等鈉鹽成分。

2.泥岩浸水後之固液相變化
　　從環境掃瞄式電子顯微鏡的觀察發現，泥岩浸水後有崩解(Slaking)、回脹及分散行為明顯減少泥岩顆粒間的孔隙。泥岩浸水後透過固相ESEM/EDX顯微結構分析及液相溶出參數分析之同步觀察，由固相ESEM/EDX顯微結構觀察發現，不同時間下浸水泥岩的顯微孔隙明顯改變。另由液相離子分析發現，特定溶出陽離子包括：Na+、Mg2+、K+及Ca2+，特定溶出陰離子包括： SO42- 及Cl-，陰陽離子中分別以SO42-及Na+離子溶出最多，泥岩遇水易於回脹崩解應為鈉鹽所引起。

3.溶出參數與夯實泥岩襯裡之自由回脹行為之關係
　　透過溶出參數與夯實泥岩襯裡自由回脹行為之同步觀察得知，夯實泥岩在初期浸水時，幾乎完全回脹，夯實泥岩早期(<3days)的自由回脹行為直接受到溶液中Na+離子濃度及CaCO3沈澱作用所致，至於夯實泥岩的晚期(>3days)微量回脹則是受Mg2+離子溶出影響。溶出參數中以Na+、SO42-離子、EC及pH與夯實泥岩襯裡自由回脹具有甚佳的相關性，顯示可以用Na+離子、SO42-離子、EC及pH等溶出參數預測夯實泥岩襯裡的自由回脹行為。

4.溶出參數與夯實泥岩襯裡受限回脹及其滲透係數之關係
　　夯實泥岩襯裡受限回脹能降低其滲透係數，且夯實泥岩襯裡滲透係數亦可由受限回脹量與滲透係數之數學模式直接預測，此外，夯實泥岩襯裡浸水>1.6day，受限回脹達穩定狀態，滲透係數亦趨於穩定，此時入滲液中的pH及Na+離子濃度等溶出參數亦接近穩定，入滲液中溶出參數中以Na+離子濃度同時能預測夯實泥岩襯裡的受限回脹及滲透係數，顯示泥岩特定鹽類的溶出促使Na+離子濃度成為預測夯實泥岩襯裡回脹及滲透行為的地工指標(Geoindicator)。

　　High exchangeable sodium percent (ESP) of mudstone is attributed to the dissolution of soluble salts from mudstone itself. As mudstone is immersed in water, the behaviors of slaking, swelling and dispersion is susceptible to occur. In other words, mudstone is watersensitive. It is controversial issue whether dissolution of salts will change geotechnical properties and engineering applications of compacted mudstone or not. Knowledge of leaching parameters is important in estimation of geotechnical behaviors for compacted mudstone liners under field conditions. In order to distinguish effects of leaching parameters on swelling and permeability behaviors of compacted mudstone liners, critical soluble salts are separated from mudstone by extraction, centrifugation, filtration, condensation and crystallization. The critical soluble salts are identified by using scanning electron microscopy (SEM) /energy-dispersive X-ray analysis (EDAX), X-ray fluorescence spectrometry (XRF), X-ray diffractometry (XRD), conductivity measurement, ion chromatography (IC), and environmental scanning electron microscopy (ESEM)/EDAX techniques. The mudstone-water mixtures at specific moment is characterized in liquid and solid phase by analyses of leaching parameters and observations of environmental scanning electron microscopy (ESEM)/EDAX, respectively. The concurrent use of the leaching parameters analysis and ESEM/EDAX examination yielded valuable information regarding the leaching parameters and microchanging characteristics of the soaked mudstone. Acceptable zone is specified by the results of compaction and permeability test. Based on acceptable zone, the standard specimens are prepared for free swelling test and confined swelling permeability test. With the concurrent analyses of leaching parameters using a pH meter, a conductivity meter, and ion chromatography (IC) techniques, the relationships among leaching parameters, swelling and permeability behavior are well established.

　　Based on the results above, the conclusion are summarized as follows:
(1) Identification of mudstone and critical soluble salts
　　Closely examining chemical characteristics indicated that mudstone is as saline-alkali soil based on ECe>4 m mho cm-1and ESP>15%. The alkaline reaction of the natural mudstone may undergo hydrolysis of Na+ ions. Owing to the results from SEM /EDX, XRF and XRD，critical soluble salts are recognized as sodic salts such as Na2SO4及NaCl.

(2) Liquid and solid phase of mudstone-water mixture
　　ESEM micrographs clearly show evidence of slaking, swelling and dispersion of mudstoneduring soaking since the visible pores are filled with small aggregative masses. Natural mudstone includes the critical soluble cations such as Na+, Mg2+, K+, and Ca2+ and anions such as SO42- and Cl-. The leaching of Na+ and SO42- ions in the early soaking period participates importantly in making water-sensitive mudstone highly susceptible to slaking and dispersion. It is suggested that swelling, slaking and dispersing behaviors of mudstone are induced by the dissolution of sodic salts.

(3) Relationships between leaching parameters and free swelling behaviors of compacted mudstone liners
　　The concurrent use of the free swell test and leaching parameters analysis yielded valuable information regarding the swelling and leaching behaviors of compacted mudstone. The swelling developed relatively rapidly after the start of soaking, stopping after 7 days. The early swelling behaviors of compacted mudstone are directly related to the concentration of Na+ ions in the soaking suspension and the precipitation of CaCO3 in compacted mudstone. Moreover, the very slightly swelling after the 3 days of soaking can be attributed to the dissolution of Mg2+ ion in compacted mudstone. The relationships of free swelling to leaching parameters indicated that the EC, pH, Na+ and SO42- ions in soaking suspension are significantly advantageous to predict the amount of free swelling for compacted mudstone liners.

(4) Relationships among leaching parameters, confined swelling and permeability behavior of compacted mudstone liners
　　Swelling of compacted mudstone liners enhances the reduction of permeability. Swelling and permeability behaviors of mudstone are steady after 1.6days. The leaching parameters such as pH and concentration of Na+ ions are also constantly after 1.6 days. The confined swelling and permeability of compacted mudstone liners can be directly estimated by leaching parameters such as concentration of Na+ ions. Based on the relationships among leaching parameters, confined swelling and permeability, it is established that confined swelling and permeability of compacted mudstone liners are well estimated from concentration of Na+ ions. Therefore, concentration of Na+ ions can be taken as geoindicators of compacted mudstone liners.。

誌謝 I
摘要 III
ABSTRACT V
總目錄 VIII
List of Figures XII
List of Tables XVI

第一章 緒論 1
　1-1 研究動機 1
　1-2 研究目的 3
　1-3 研究內容 5

第二章 文獻回顧 7
　2-1　泥岩材料 7
　　2-1-1　分佈 7
　　2-1-2　顆粒大小 11
　　2-1-3　黏土礦物 11
　　2-1-4　工程應用 14
　　2-1-5　崩解機制 19
　2-2　天然土壤襯裡 22
　　2-2-1　黏土礦物與滲出水之相容性 25
　　2-2-2　天然土壤襯裡之材料規範 27
　　2-2-3　施工鋪設之可接受區 30
　2-3 土壤回脹及滲透 33
　　2-3-1 土壤回脹基本理論 33
　　2-3-2　土壤回脹機制及其影響因子 35
　　2-3-3　土壤滲透基本理論 39
　　2-3-4　土壤滲透機制及其影響因子 44
　2-4　土壤溶出參數 45
　　2-4-1　導電度 46
　　2-4-2　陽離子 46
　　2-4-3　鈉吸附比 47
　　2-4-4　陰離子 47　
　　2-4-5　pH 48
　2-5　土壤回脹及滲透行為與溶出參數之相互關係 48
　　2-5-1 土壤回脹與滲透之關係 48
　　2-5-2 溶出參數與土壤回脹之關係 50
　　2-5-3 溶出參數與土壤滲透之關係 51

第三章　實驗材料與方法 54
　3-1　實驗設計 54
　3-2　實驗材料及配製 56
　　3-2-1　實驗材料 56
　　3-2-2　實驗室試體製作 57
　　3-2-3　藥品配製 64
　　3-2-4　實驗設備 67
　3-3　分析技術 75
　　3-3-1　元素及晶相分析 75
　　3-3-2　顯微結構分析 75
　3-4　實驗方法 76
　　3-4-1　泥岩襯裡材料物化特性分析 76
　　3-4-2　泥岩浸水後之固液相分析 80
　　3-4-3　自由回脹試驗及溶出參數分析 82
　　3-4-4　受限回脹滲透試驗及溶出參數分析 84

第四章 結果與討論 88
　4-1　天然泥岩基本物化特性 88
　　4-1-1　天然泥岩之物理特性 88
　　4-1-2　天然泥岩之化學特性 88
　　4-1-3　天然泥岩顯微結構及元素組成 92
　　4-1-4　天然泥岩礦物組成 92
　4-2 天然泥岩特定溶出鹽類鑑定 96
　　4-2-1 SEM/EDX顯微結構及元素分析 96
　　4-2-2 X光繞射分析 98
　　4-2-3 泥岩浸水後固相ESEM/EDX顯微結構分析 101
　　4-2-4 泥岩浸水後液相溶出參數分析 108
　4-3 溶出參數對夯實泥岩襯裡自由回脹行為之影響 111
　　4-3-1 夯實泥岩襯裡之自由回脹行為 114
　　4-3-2 夯實泥岩襯裡之溶出行為 114
　　4-3-3 夯實泥岩襯自由回脹量與溶出參數之模式建立 124
　4-4 溶出參數對夯實泥岩襯裡受限回脹及滲透行為之影響 132
　　4-4-1 夯實泥岩襯裡之受限回脹行為 132
　　4-4-2 夯實泥岩襯裡之滲透行為 132
　　4-4-3 夯實泥岩襯裡之溶出行為 134
　　4-4-4 夯實泥岩受限回脹與溶出參數之模式建立 144
　　4-4-5 夯實泥岩滲透係數與溶出參數之模式建立 147

第五章 結論與建議 152
　5-1 泥岩及其特定溶出鹽類鑑定 152
　5-2 泥岩浸水後之固液相變化 152
　5-3 溶出參數與夯實泥岩襯裡自由回脹行為 153
　5-4 溶出參數對受限夯實泥岩襯裡回脹及滲透行為之影響 153
　5-5 建議 154

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