硫鋁酸鈣水泥複合膠結材之配比與工程性質之研究

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張辰鴻(Chen-Hong Zhang) 查詢紙本館藏

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土木工程學系

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硫鋁酸鈣水泥複合膠結材之配比與工程性質之研究
(Research of Calcium Sulfoaluminate Cement Composite Binder For Proportion and Engineering Properties)

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至系統瀏覽論文 (2028-6-1以後開放)

摘要(中)

硫鋁酸鈣水泥為一種以硫鋁酸鈣(又稱葉綠石，簡寫為C4A3S̅)、矽酸二鈣(又稱貝萊土，簡寫為C2S)及鋁鐵酸四鈣(C4AF)為主要成分組成之特殊水泥，具有早期強度發展快速、凝結時間短、流動性佳及乾縮量小等性質，因應其化學反應及經濟性之考量，需以硫鋁酸鈣水泥熟料(簡稱CSA)、卜特蘭Ⅰ型水泥(簡稱OPC)及無水石膏(簡稱CS̅ )互相調配成硫鋁酸鈣水泥複合膠結材。
本研究將分為「材料參數對水泥漿體水化特性及強度發展之影響」、「CSA水泥砂漿工程性質研究」、「CSA水泥砂漿多元關係建立」三階段進行探討。第一階段主要以固定0.30之水膠比製備水泥漿體，分別根據二元膠結材系統(CSA - CS̅ 系統、OPC - CSA系統)及三元膠結材系統(OPC - CSA - CS̅ 系統)之不同配比組合，評估材料間交互影響性，並探討不同材料比例關係與水化特性之關係及其作為超早強水泥之發展潛力；第二階段主要以水泥砂漿驗證其水化特性及硬固特性，並以強度發展及耐久性評估CSA水泥複合膠結材是否符合ASTM C1600 標準要求(分為四項等級，強度由高至低依序為URH、VRH、MRH、GRH)；第三階段則主要以非破壞檢測法針對於一天齡期內之結果，建立其與CSA水泥複合膠結材強度發展之關係，同時評估材料比例與其水化特性、硬固性質及耐久性質之相互關係，並以此建立三元相圖。
水泥漿體方面，CSA - CS̅ 系統中之CS̅ 比例增加時可利於其早期及晚期之強度發展，水膠比0.30之水泥漿試體在3小時最高可達到68 MPa，於28天齡期時仍可有大於110 MPa之抗壓強度表現，同時，CS̅添加量充足 (CS̅/CSA = 1/2、1/3)時可符合ASTM C1600之凝結時間要求。於OPC – CSA 複合膠結材系統中，CSA含量高於20 % 時，其終凝時間將小於10分鐘，其早期(24小時內)強度發展呈隨CSA含量上升而提高之趨勢，在含量高於25 % 時可具有較佳超早強水泥發展潛力，但於齡期達1天後之強度發展則隨CSA含量增加而下降。
水泥砂漿方面，CSA - CS̅系統(CS̅/CSA = 1/2、1/3、1/4、1/5)皆可滿足ASTM C1600中之MRH等級之強度要求，而OPC – CSA及OPC - CSA - CS̅系統以高CSA含量及高CS̅比例表現為佳，其中以配比OPC = 70 % 、CS̅/CSA = 1/2時，可符合MRH(中度早強型, Medium Rapid Hardening)等級之強度要求，配比OPC = 70 % 、CS̅/CSA = 1/3則具備近GRH等級之強度表現；耐久性質方面，依優劣排序分別為CSA - CS̅系統> OPC > OPC - CSA - CS̅系統> OPC – CSA 系統> CSA。
非破壞性檢測方面，以成熟度法評估水泥漿體之抗壓強度關係性時，二者之關係於3小時及6小時具備良好之相關性(R2 ＞ 0.8)；但作為24小時後之強度檢測方法較不準確(R2 = 0.1 ~ 0.8)；而超音波波速法評估水泥漿體之抗壓強度具備較強之相關性(R2 ＞ 0.95)，顯示其作為強度檢測方法具有可行性；由三元相圖討論各配比於不同性質之關係時，可以較少之配比進行試驗，預測其於相同水膠比條件下，其餘未進行試驗配比餘同齡期之下不同配比之結果，並且得以色塊之顏色判斷其趨勢。

摘要(英)

Calcium sulfoaluminate cement is a kind of calcium sulfoaluminate (C4A3S̅), dicalcium silicate (also known as Belite soil, abbreviated as C2S) and tetracalcium aluminum ferrite (C4AF). The special cement composed of ingredients has the properties of rapid early strength development, short setting time, good fluidity and small dry shrinkage. In consideration of its chemical reaction and economical considerations, calcium sulfoaluminate cement clinker (CSA) is required , Portland Type I cement (OPC) and anhydrous gypsum (CS̅) are blended together to form calcium sulfoaluminate cement composite cement.
This study will be divided into three phases: "the influence of material parameters on the hydration characteristics and strength development of cement paste", "research on engineering properties of CSA cement mortar", and "establishment of multiple relationship of CSA cement mortar". The first stage is mainly to prepare cement slurry with a fixed water-binder ratio of 0.30, according to the difference between the binary binder system (CSA - CS̅ system, OPC - CSA system) and the ternary binder system (OPC - CSA - CS̅ system) Proportion combination, evaluate the interaction between materials, and explore the relationship between the ratio of different materials and hydration characteristics and its development potential as super early strength cement; the second stage mainly uses cement mortar to verify its hydration characteristics and hardening characteristics , and evaluate whether the CSA cement composite binder meets the requirements of the ASTM C1600 standard based on safety and durability; the third stage mainly uses non-destructive testing methods to establish the strength development of the CSA cement composite binder based on the results within one day of age At the same time, evaluate the relationship between the proportion of materials and their hydration properties, hard solid properties and durability properties, and establish a ternary phase diagram.
In terms of cement paste, increasing the proportion of CS̅ in the CSA-CS̅ system can be beneficial to its early and late strength development. The cement slurry specimen with a water-binder ratio of 0.30 can reach a maximum of 68 MPa in 3 hours, and it is still strong at 28 days. It can have a compressive strength greater than 110 MPa. At the same time, when the amount of CS̅ is sufficient (CS̅/CSA = 1/2, 1/3), it can meet the setting time requirements of ASTM C1600. In the OPC-CSA composite binder system, when the CSA content is higher than 20%, its final setting time will be less than 10 minutes, and its early (within 24 hours) strength development tends to increase with the increase of CSA content. When it is 25%, it can have better development potential of super early strength cement, but the strength development after 1 day of age will decrease with the increase of CSA content.
For cement mortar, the CSA - CS̅ system (CS̅/CSA = 1/2, 1/3, 1/4, 1/5) can meet the strength requirements of the MRH grade in ASTM C1600, while OPC - CSA and OPC - CSA - The CS̅ system performs best with high CSA content and high CS̅ ratio. Among them, when the ratio of OPC = 70 % and CS̅/CSA = 1/2, it can meet the strength requirements of the MRH grade. The ratio of OPC = 70 % and CS̅/ CSA = 1/3 means that it has a strength performance close to GRH level; in terms of durability, the order of durability is CSA - CS̅ system > OPC > OPC - CSA - CS̅ system > OPC - CSA system > CSA.
In terms of non-destructive testing, when the maturity method is used to evaluate the relationship between the compressive strength of cement paste, the relationship between the two has a good correlation at 3 hours and 6 hours (R2 > 0.8); but as the strength after 24 hours The detection method is relatively inaccurate (R2 = 0.1 ~ 0.8); and the ultrasonic wave velocity method has a strong correlation (R2 > 0.95) in evaluating the compressive strength of cement paste, which shows that it is feasible as a strength detection method; When discussing the relationship between various proportions and different properties in the meta-phase diagram, it is possible to conduct experiments with fewer proportions, and predict the results of other proportions that have not been tested under the same age and different proportions under the same water-cement ratio conditions. And the trend can be judged by the color of the color block.

關鍵字(中)

★ 硫鋁酸鈣水泥
★ 早強水泥
★ 水泥複合膠結材
★ 鈣釩石

關鍵字(英)

★ calcium sulfoaluminate cement
★ early strength cement
★ calcium sulfoaluminate cement binder
★ Ettringite

論文目次

摘要 i
Abstract iii
致謝 v
目錄 ii
圖目錄 vi
表目錄 xii
第 1 章緒論 1
1.1 研究背景與動機 1
1.2 研究目的 2
1.3 研究內容 3
第 2 章文獻回顧 5
2.1 超早強水泥規範及使用要求 5
2.1.1 超早強水泥定義及要求 5
2.1.2 超早強水泥種類 6
2.1.3 超早強水泥應用 7
2.2 硫鋁酸鈣水泥分類及特性 9
2.2.1 硫鋁酸鈣水泥分類及定義 9
2.2.2 硫鋁酸鈣水泥機理 11
2.3 卜特蘭水泥 12
2.3.1 卜特蘭水泥定義 12
2.3.2 卜特蘭水泥水化機理 13
2.4 石膏(無水石膏、半水石膏、二水石膏) 14
2.5 多元膠結材系統 17
2.5.1 CSA - CS二元膠結材系統 18
2.5.2 OPC – CSA及OPC – CSA - CS 多元膠結材系統 19
2.6 物理化學性質影響 20
2.6.1 水泥凝結時間 20
2.6.2 強度成長 22
2.6.3 體積穩定性 24
2.6.4 水化熱 27
2.6.5 硫酸鹽侵蝕 29
2.7 非破壞檢測法與抗壓強度關係 31
2.7.1 反彈錘法 32
2.7.2 貫入阻力法 32
2.7.3 拉拔試驗量測法 33
2.7.4 超音波波速量測法 33
2.7.5 成熟度法 35
2.8 抗壓強度及抗彎強度關係 36
第 3 章研究規劃 39
3.1 試驗規劃及目的 39
3.2 材料基本性質 41
3.3 CSA水泥基材水化特性及性質發展 46
3.3.1 CSA水泥基材配比及試驗編號 49
3.3.2 基本試驗項目 51
3.3.3 水化機理研究 55
3.4 CSA水泥砂漿工程性質研究 59
3.4.1 水泥砂漿配比 62
3.4.2 水泥砂漿拌和程序 64
3.4.3 水泥砂漿強度及工作性探討 64
3.4.4 耐久性試驗 66
3.4.5 水化特性及強度發展推演 67
第 4 章試驗結果 71
4.1 CSA水泥基材水化特性及發展 71
4.1.1 水泥漿體單位重 74
4.1.2 凝結時間 75
4.1.3 水泥漿體抗壓強度 79
4.1.4 水化24小時內升溫放熱曲線 88
4.1.5 CSA水泥基材超音波波速試驗 90
4.1.6 CSA水泥基材成熟度 95
4.1.7 結晶形貌-SEM試驗 100
4.1.8 內部緻密性及孔隙分布狀態 107
4.1.9 熱壓膨脹試驗 109
4.1.10 CSA水泥基材水化特性及發展小結 111
4.2 CSA水泥砂漿工程性質研究 114
4.2.1 水泥砂漿流度 116
4.2.2 水泥砂漿抗壓強度 116
4.2.3 水泥砂漿抗彎強度 121
4.2.4 耐久性質 124
4.2.5 CSA水泥砂漿工程性質研究小結 130
4.3 CSA水泥砂漿多元關係建立 132
4.3.1 水化特性 132
4.3.2 強度發展 134
4.3.3 水泥砂漿抗壓及抗彎強度關係 134
4.3.4 比較成熟度法及超音波波速試驗法 138
4.3.5 三元相圖推演 140
4.4 綜合討論 145
4.4.1 CSA - CS二元膠結材系統配比 145
4.4.2 OPC – CSA及OPC – CSA - CS 多元膠結材系統配比 145
第 5 章結論及建議 147
5.1 結論 147
5.2 建議 148
參考文獻 151
圖附錄 158
表附錄 160

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指導教授

王韡蒨(Wei-Chien Wang)

審核日期

2023-7-26

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