臺灣博碩士論文加值系統

深共熔溶劑(Deep Eutectic Solvents, DES)作為新一代的離子液體，它具有具原物料便宜、合成簡單、無毒、可生物降解、不易燃、不易揮發、高黏度、容易儲存、良好溶解性等優點，DES有潛力可以取代傳統水溶液，作為新一代有機無機溶劑。超臨界二氧化碳具有低黏性、低表面張力、高擴散性的特性，使用於電鍍液時，鍍層有較好的覆蓋性及均勻性並可增加鍍層的硬度。而本研究使用氯化膽鹼與尿素以1:2莫爾比混合之深共熔溶劑作為電鍍鎳的電解液並結合超臨界二氧化碳，研究發現使用深共熔溶劑比傳統水溶液擁有較高的鍍層硬度，而超臨界二氧化碳又比一般電鍍鍍層硬度來的更高；由於超臨界二氧化碳的低表面張力的特性，使得超臨界電鍍比一般電鍍擁有較好的表面粗糙度；隨著溫度的上升，離子傳遞的效能越好使電流效率上升。而添加糖精在超臨界電鍍下可以改善電鍍效率、降低晶粒大小、表面粗糙度、降低內應力及提高耐腐蝕性。

Deep eutectic solvent (DES) is a new generation of ionic liquids. It has the advantages of cheap raw materials, simple synthesis, non-toxic, biodegradable, non-flammable, non-volatile, high viscosity, easy to store and good solubility. DES has the potential to replace traditional aqueous solutions as a new generation of organic and inorganic solvents. Supercritical CO2 has low viscosity, low surface tension and high diffusivity. The coating prepared in supercritical CO2 environment has good coverage and uniformity. The supercritical CO2 process can increase the hardness of the coating when used in electroplating solution. In this study, DES from the mixture of choline chloride and urea in 1:2 molar ratio and supercritical carbon dioxide was used as the electrolyte for electroplating nickel. Our study has found that the Ni coating prepared in the DES has a higher hardness than conventional aqueous solutions. Moreover, with the introduction of supercritical carbon dioxide further increased the coating’s hardness than its conventionally electroplated counterpart. Due to the low surface tension properties of supercritical carbon dioxide, the electroplated Ni coating has better surface roughness than conventional plating. The raise in the DES electrolyte temperature increased the current efficiency in plating because of the higher ion transfer efficiency. Adding saccharin in supercritical plating can improve current efficiency, lower grain size, surface roughness, internal stress and raise corrosion resistance.

摘要 i
Abstract ii
誌謝 iv
目錄 v
表目錄 viii
圖目錄 ix
第一章 前言 1
1.1 離子液體之發展 1
1.2 深共熔溶劑之發展 2
1.3 研究動機與目的 2
1.4 論文架構 4
第二章 基礎理論與文獻回顧 5
2.1 電化學沉積 5
2.1.1 電化學沉積原理 5
2.1.2 電化學質傳 7
2.1.3 電化學結晶的成長過程 7
2.1.4 影響鍍層的結構主要因素 9
2.1.5 鍍層的結構與性質 10
2.1.6 電鍍時間與鍍層厚度控制 11
2.2 超臨界相 12
2.2.1 超臨界流體 12
2.2.2 超臨界二氧化碳 12
2.2.3 超臨界電鍍文獻回顧 13
2.3 深共熔溶劑 15
2.3.1 深共熔溶劑的定義 15
2.3.2 深共熔溶劑文獻回顧 17
第三章 實驗方法及設備 19
3.1 實驗流程 19
3.1.1 超臨界二氧化碳電鍍實驗設備 20
3.1.2 一般電鍍實驗設備 21
3.1.3 電鍍實驗藥品 23
3.1.4 電鍍液之調配 23
3.1.5 試片前處理 25
3.2 實驗參數設定 26
3.3 二氧化碳濃度檢測 28
3.3.1 實驗流程 28
3.4 鍍層微結構分析 29
3.4.1 穿透式電子顯微鏡 29
3.4.2 掃描式電子顯微鏡 30
3.4.3 X-光繞射儀 31
3.4.4 電子微探儀 33
3.5 機械性質分析 34
3.5.1 表面輪廓儀 34
3.5.2 維克氏硬度試驗機 35
3.5.3 鍍層內應力量測 36
3.6 鍍層電化學特性分析 38
第四章 結果與討論 41
4.1 深共熔溶劑二氧化碳濃度與水溶液的比較 41
4.2 鍍層表面形貌及微結構分析 42
4.2.1 鍍層成份分析 42
4.2.2 試片表面形貌 47
4.2.3 鍍層電流效率 48
4.2.4 鍍層微結構 50
4.2.5 鍍層內部結構 57
4.2.6 X-光繞射圖譜 59
4.2.7 XRD分析鍍層晶粒大小 62
4.3 鍍層機械性質分析 64
4.3.1 鍍層表面粗糙度 64
4.3.2 鍍層維克氏硬度量測 67
4.3.3 鍍層內應力量測 70
4.4 鍍層電化學分析 72
第五章 結論 77
5.1 不同溫度及糖精對鍍層微結構之影響 77
5.2 不同溫度及糖精對鍍層機械性質之影響 77
5.3 不同溫度及糖精對鍍層電化學影響 78
5.4 深共熔溶劑在超臨界電鍍下之優缺點 79
5.5 未來展望 80
參考文獻 81

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