本研究的主要目的是開發於乳化超臨界二氧化碳(sc-CO2)流體中電鍍鎳磷合金的技術，並比較所製備之鍍層與在傳統常壓電鍍所製備的鎳磷合金鍍層性質的差異。鍍液乳化所需添加界面活性劑的種類、添加濃度對電鍍製程及鍍層性質的影響，是重要研究的重點。鍍層經過450℃熱處理一小時後之性質變化，亦是本論文探討之課程之一。鍍層性質之分析採用多種分析方法，包含掃描式電子顯微鏡(SEM)觀察表面形貌、原子力顯微鏡(AFM)量測鍍層粗糙度、X-ray繞射儀(XRD)分析鍍層結晶結構、維氏硬度計量測鍍層硬度值，並且使用恆電位儀(Potentiostat)分析鍍層電化學性質。
本論文中採用之界面活性劑分別為C12EO8、FSN以及EO17PO14，研究結果顯示，常壓下所得鍍層表面具有許多孔洞缺陷，而引入sc-CO2於電鍍系統中並添加界面活性劑，則可得到無孔洞與針孔缺陷且平整的鍍層表面。由於FSN的親二氧化碳端的能力較佳，較容易使sc-CO2與水溶液互溶形成乳化狀態，只需要添加微量的界面活性劑即可使二氧化碳與水形成一均勻的乳化相，使鍍層呈現一平整的表面，而C12EO8與EO17PO14則是需要添加較高濃度才可達到較佳的乳化效果。然而由於sc-CO2造成鍍液pH值下降，使得鍍層析鍍速率變慢且鍍層磷含量下降。
XRD與鍍層硬度值分析結果顯示，以C12EO8為乳化劑的sc-CO2製程可得到結晶性較佳、鍍層硬度值較高且具有良好耐磨耗性質的鎳磷合金鍍層，並且經過450℃熱處理一小時後，常壓與超臨界鍍層都有Ni3P相的析出，更可提升其耐磨耗性且鍍層硬度值可高達949 Hv。
電化學極化曲線量測結果顯示，在1M氫氧化鈉水溶液當中，Ni-P合金鍍層表面會發生鈍化現象。而在1M鹽酸水溶液中，於含有sc-CO2環境中所得鍍層與在常壓下所得鍍層比較，其腐蝕電位較高，而腐蝕電流密度則較低。經過熱處理後，在1M鹽酸水溶液環境中，常壓與sc-CO2流體中析鍍所得的鎳磷合金鍍層的腐蝕電流密度都有下降的趨勢。

The electrodeposition of Ni-P films with the co-existenc of supercritical carbon dioxide (sc-CO2) fluid was investigated. The effects of different types of surfactant and their concentration on the electrodeposition behavior were focused. Material properties of the as-deposited films fabricated in the normal and ambient pressure electrolyte and those from the sc-CO2 bath were analyses and compared. The effect of heat treatment at 450 ℃ for 1 hour on the changes of material properties of the deposited Ni-P coatings was also explored. The techniques employed for material characterization include (1) scanning electron microscopy (SEM) for surface morphology examination, (2) atomic force microscopy (AFM) for surface roughness determination, (3) X-ray diffraction (XRD) for crystal structure analysis, and (4) Vicker’s hardness measurement. The electrochemical behavior of the deposited film was investigated by employing a potentiostat.
The surfactants used in this study were C12EO8, FSN and EO17PO14. The experimental results showed that voids and pinholes were commonly found in the Ni-P film electrodeposited in conventional bath at ambient bath. However, these defects could be eliminated when electrodeposition was conducted in the emulsified sc-CO2 bath with proper addition of surfactant. Due to its better affinity to sc-CO2, only a small amount of FSN addition (0.1 vol. %) was sufficient to emulsify sc-CO2 with aqueous electrolyte and gave rise to a deposit with smooth surface morphology. In contrast, a higher concentration of C12EO8 or EO17PO14 was required to obtained an emulsified bath. In all cases, the low pH of the bath resulting from the presence of sc-CO2 fluid caused a lower deposition rate and a lower phosphorus content in the Ni-P film.
The experimental results from XRD analysis and hardness measurement indicated that a Ni-P film with higher crystallinity, higher hardness and better wear resistance could be obtained by electrodeposition from emulsified sc-CO2 bath with C12EO8 as the surfactant, as compared with that from conventional process. Heat treatment at 450 oC for 1 hour resulted in precipitation of Ni3P in the substrate, which gave rise to a harness as high as 950 Hv and improved the wear resistance.
The potentiodynamic polarization curves showed that Ni-P film could be passivated easily in 1 M NaOH solution, almost independent of the bath used. In 1 M HCl solution, however, the Ni-P film deposited from the emulsified sc-CO2 bath had a higher corrosion potential with a lower corrosion current density as compared with that of conventional deposit. Regardless of the deposition bath, heat treatment led to a reduction of corrosion current density of all the Ni-P films in 1 M HCl solution.

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