臺灣博碩士論文加值系統

響應近年發展綠色科技趨勢，為降低傳統電鍍以及離子溶液對於環境危害並朝向永續環保發展，許多研究替代具有高表面硬度、耐磨耗、成本低廉卻對人體健康、環境污染有重大影響的金屬鉻鍍層。文獻指出鎳基材料在硬度、耐磨耗、抗腐蝕等方面因性能優秀而受到關注，其中鎳鎢合金(Ni-W alloy)在鎳基金屬具有的優點上表現更加突出，被視為能夠替代鉻鍍層的潛在備選材料之一。有鑒於此，本研究選用對環境友善的深共熔溶液(Deep-Eutectic Solvent, DES)作為電鍍主要溶劑，並以硫酸鎳、鎢酸鈉、檸檬酸、硼酸混合製備綠色電鍍液。探討在一般電鍍與超臨界二氧化碳電鍍製備之鎳鎢合金鍍層之材料性質，分析鎳鎢鍍層在表面形貌、機械性質及耐腐蝕性等方面之表現，期望發展出以環境友善為主軸且業界可應用之嶄新電鍍製程。鍍層檢測包括以掃描式電子顯微鏡(Scanning Electron Microscope, SEM)觀察鎳鎢合金鍍層之表面形貌，確認表面有無明顯龜裂；以動電位極化曲線檢測不同電流密度及電鍍方式下製備鍍層的抗腐蝕性質。以能量散射光譜儀(EDS)檢測鍍層成分，發現超臨界二氧化碳電鍍製備之鍍層，鎢原子百分比最高為0.44%，高於一般電鍍所得最高之0.21%，分析元素分佈觀察到鎢原子於鍍層內呈少量均勻分布；在硬度檢測中，發現超臨界二氧化碳電鍍之鎳鎢鍍層硬度最大為630 HV，一般電鍍最大為545 HV，二者相較純鎳鍍層334 HV分別有94.6%與63.2%的提升；在耐腐蝕性檢測中，一般電鍍之鎳鎢鍍層具有最低腐蝕電流密度，相較於超臨界二氧化碳鍍層低約69 %，於純鎳鍍層約41%；兩種電鍍製程及不同電流參數下，鎳鎢鍍層表面皆呈現鋼灰色，結晶方位以(211)或(220)為主。

Responding to the recent trends in green technology, this study investigates environmentally sustainable alternatives to conventional chromium plating, which is known for its adverse effects on human health and environmental pollution. Nickel-based materials, particularly Nickel-Tungsten (Ni-W) alloys, are recognized for their superior properties in terms of hardness, wear resistance, and corrosion resistance, making them promising substitutes for chromium coatings. In this research, a green electroplating solution is prepared using an environmentally friendly Deep-Eutectic Solvent (DES) as the primary electrolyte, mixed with nickel sulfate, sodium tungstate, citric acid, and boric acid. The material properties of Ni-W alloy coatings are explored under conventional and supercritical carbon dioxide (SC-CO2) electroplating conditions. The study aims to develop a new electroplating process centered on environmental friendliness and applicable to industry standards. Coating evaluation included surface morphology assessments via Scanning Electron Microscopy (SEM), which confirmed the absence of significant cracks; corrosion resistance was measured through dynamic potential polarization curves across different current densities and plating methods. Energy-dispersive X-ray spectroscopy (EDS) was utilized to analyze the composition of the coatings, revealing a maximum tungsten content of 0.44% in SC-CO2 coating, which is significantly higher than the 0.21% achieved with Conventional coating. The elemental distribution analysis showed a uniform distribution of tungsten atoms within the coating. In hardness tests, the maximum hardness of the Ni-W coatings prepared by supercritical carbon dioxide electroplating is found to be 630 HV, compared to 545 HV for conventional electroplating, representing a 94.6% and 63.2% increase over pure nickel coatings at 334 HV, respectively. In corrosion resistance testing, the Ni-W coating produced by conventional electroplating exhibited the lowest corrosion current density, approximately 69% lower than the SC-CO2 coating, and about 41% lower than pure nickel coatings. Both electroplating processes resulted in steel-gray coatings with a crystalline orientation of (211) or (220).

摘要 i
ABSTRACT iii
誌謝 v
表目錄 ix
圖目錄 x
第一章 前言 1
1.1 研究背景 1
1.2 研究動機與目的 2
1.3 論文架構 4
第二章 文獻回顧 5
2.1 電化學沉積 5
2.1.1 電化學結晶成核與成長過程 7
2.1.2 影響電鍍鍍層之因素 8
2.2 鎳鎢合金 10
2.2.1 誘導共沉積 10
2.2.2 合金電鍍之電解定律與電流效率 12
2.2.3 鎳鎢合金薄膜文獻 13
2.3 深共熔溶液 16
2.3.1 離子溶液與深共熔溶液 16
2.3.2 深共熔溶劑於電鍍之文獻回顧 18
2.4 超臨界流體 21
2.4.1 超臨界二氧化碳 22
2.4.2 超臨界二氧化碳於電鍍之文獻回顧 23
第三章 實驗方法 27
3.1 實驗架構 27
3.1.1 實驗使用藥品 28
3.1.2 鎳鎢電鍍液調配 29
3.1.3 陰極、陽極材料前處理 31
3.1.4 實驗製程參數 34
3.2 一般電鍍製程之實驗設備 35
3.3 超臨界二氧化碳電鍍實驗設備 36
3.4 鍍層微結構分析 39
3.4.1 掃描式電子顯微鏡 39
3.4.2 X-光繞射分析儀 43
3.5 鍍層機械性質分析 46
3.5.1 維小維克氏硬度試驗分析 46
3.5.2 表面粗糙度 47
3.5.3 刮痕試驗儀 49
3.6 鍍層電化學檢測 50
第四章 結果與討論 52
4.1 鍍層微結構與表面形貌分析 52
4.1.1 鍍層表面形貌 52
4.1.2 鍍層表面形貌顯微觀察 54
4.1.3 鍍層橫截面形貌與厚度觀察 57
4.1.4 鍍層成分定量與橫截面元素分佈分析 60
4.1.5 鍍層電流效率 63
4.2 鍍層之維氏硬度分析 65
4.3 鍍層之刮痕試驗分析 67
4.4 鍍層之電化學分析 69
4.5 X光繞射圖譜與晶粒尺寸分析 71
第五章 結論與未來展望 74
5.1 結論 74
5.1.1 鍍層表面形貌與微結構 74
5.1.2 鍍層機械性質分析 75
5.1.3 鍍層電化學性質 75
5.2 未來展望 76
參考文獻 77

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