臺灣博碩士論文加值系統

本論文探討AZ91D鎂合金微弧氧化製程在矽酸鹽類電解液系統與鋯酸鹽類電解液系統所形成之氧化膜特性，在固定頻率500 Hz及陽極400 V、陰極50 V之工作電壓下改變占空比及鍍膜工作時間，對陶瓷氧化膜微觀結構、膜厚、硬度表現、鍍膜相結構和電化學耐蝕特性進行研究。
在矽酸鹽電解液中，發現占空比的增加使得工作電流變大，而工作電流的大小正比於氧化膜之成長速率，當占空比大於20%時，過快的成膜速率使得鍍膜表面粗糙度上升，表面孔洞變大，而過大的能量使得基材表面產生局部燒蝕的情況，因此氧化膜之相結構由穩定的MgO及Mg2SiO4逐漸變成SiO2、Mg2SiO4及MgSiO3等，從SiO2的生成可知，表面電弧溫度高過SiO2之熔點1650℃，過高之溫度使得鎂離子與電解液中矽酸根燒結產生MgSiO3二次相；而較長的工作時間使得電荷累積的程明顯變大，反應劇烈的電弧因熱應力釋放使氧化膜與基材介面處產生裂痕，此裂痕將影響氧化膜之耐蝕表現，由實驗結果顯示此系列氧化膜特性表現較佳之參數為工作時間30分鐘，占空比30%時有最佳硬度(431 HV)，而工作時間10分鐘，占空比10% (4.18 x106 Ω‧cm2)時耐蝕表現最佳。
在鋯酸鹽電解液系統中，占空比對電流影響較小且無明顯規律，此系統之氧化膜成長速率較慢，有效鍍膜之占空比範圍較廣(5%~70%)，當占空比超過30%以上，氧化膜表面粗糙度大幅提升；當占空比達70%時，試片表面電弧反應劇烈，氧化膜無法緻密堆積，產生局部燒蝕造成氧化膜剝落，但在較長之工作時間下，不會產生基材與氧化膜介面龜裂情形。鋯酸鹽電解液系統中形成之氧化膜相結構主要為Mg2Zr5O12及t-ZrO2所組成，當占空比達50及70%，t-ZrO2訊號明顯，並且有較明顯之MgF2訊號出現，另外高能量電弧也使鎂合金表面變成熔融狀態，進而與電解液中氟鋯酸根反應形成Mg2Zr5O12，此結構的出現可以得知，氧化鎂固溶進入氧化鋯結構中，形成類似安定化效果。由實驗結果可知此系列氧化膜特性表現較佳之參數為工作時間30分鐘，占空比為70%時獲得最佳硬度(708 HV)，而工作時間30分鐘，占空比10% 的耐蝕表現最佳(1.02 x106 Ω‧cm2)。
整體來說，微弧氧化所形成之氧化膜有著良好的保護作用，在未經由浸泡前，矽酸鹽類電解液系統氧化膜耐蝕性較鋯酸鹽電解液系統佳，因為表面孔洞及裂痕其況較輕微，然而兩電解液系統氧化膜經由不同時間的浸泡後，發現氧化膜衰退速度不一，因兩系統所形成之氧化膜相結構的差異而有所改變，由實驗中得知，氧化膜中的相結構與分布情形在耐蝕表現上為一大關鍵，因其兩系統氧化膜中氧化鎂含量不同，使得矽酸鹽系統氧化膜阻抗衰退快，在浸泡20~30小時失重大幅增加，表面開始有大面積破裂面產生；而鋯酸鹽系統氧化膜以化學穩定性較高的Mg2Zr5O12及t-ZrO2為主，因此阻抗衰退速度較慢，鍍膜壽命較長。

In this study, the characteristics of the oxide film coated on magnesium alloy AZ91D are discussed using silicate-based and zirconate-based electrolyte system. The microstructure, phase composition, oxide hardness and corrosion resistance of the MDO coatings were discussed by adjusting duty ratio and working time under constant frequency (500 Hz) and working voltage(400 V/-50 V).
In the silicate-based electrolyte system, the higher duty ratio results in the high working current. Besides, the working current is proportional to the oxide growth rate. When the duty ratio is larger than 20%, greater oxide growth rate leads to the increasing surface roughness and enlarges the size of micro-pores. Exaggeration energy leads to partially ablation around the substrate surface, hence the phase structures of the oxide coating transform from MgO and Mg2SiO4 to SiO2, Mg2SiO4 and MgSiO3 alternatively in the silicate-based electrolyte system. From the formation of SiO2 revealed that the local micro-arc temperature was almost up to 1650℃, and so did the existence of MgSiO3.It is also found that the severe level of electric charge accumulation deteriorated the coatings during a long anodic working time. Due to release of thermal stress, the cracks form on the coating surface which has a great influence on mechanical properties and corrosion behavior. In summary, the best parameters for the oxide with optimum mechanical properties are 30% and 30 minutes(431 HV), and the most anti-corrosive one is 10% and 10 minutes (4.18 x106 Ω‧cm2) in the silicate-based electrolyte system.
On the other hand, the zirconate-based electrolyte system seldom exhibit linear regular relationship between duty ratio and working current. The growth rate of oxide coating is much slower compared to that in silicate-based electrolyte system. However, the operation range for MDO process using zirconate-based electrolyte is wide (5%~70%). Larger duty ratio results in cracks and roughness on surface. When the duty ratio is up to 70%, the coating can’t accumulate densely owing to the vigorous arc, but the oxide doesn’t strip from substrate. According to XRD pattern, the main phases in the coating are Mg2Zr5O12 and t-ZrO2 for MDO specimens in the zirconate-based electrolyte system. The intensity of t-ZrO2 and MgF2 becomes obvious at larger duty ratio(70%). Besides, the existence of Mg2Zr5O12 represents that MgO solutes into ZrO2 and stabilizes it. To sum up, the best parameters for the oxide with optimum mechanical properties are 70% and 30 minutes(708 HV), and the most anti-corrosive one is 10% and 30 minutes (1.02 x106 Ω‧cm2) in the zirconate-based electrolyte system.
Electrochemical corrosion tests indicate that the phase contents of MDO coating has a significant effect on the degradation process of coated magnesium alloy in the 3.5 wt% NaCl corrosive environment. The MDO coating in the silicate-based electrolyte system composed of MgO suffered from pitting corrosion in the twenty hours immersion test, whereas the MDO coating with ZrO2 compounds shows a much superior stability during the corrosion tests and provides an efficient corrosion protection for long period of time.

中文摘要 I
ABSTRACT III
目錄 V
圖目錄 VIII
表目錄 XIII
第一章 前言 1
第二章 研究背景與文獻回顧 3
2.1 鎂合金簡介 3
2.1.1 鎂合金的發展與特性 3
2.1.2 鎂合金的分類與命名 6
2.1.3 鎂合金的腐蝕行為 10
2.1.4 鎂合金的腐蝕機制[9] 12
2.1.5 鎂及其合金之表面耐蝕處理 20
2.2 微弧氧化法簡介 25
2.2.1 微弧氧化法之發展歷史與未來應用 25
2.2.2 微弧放電工作原理 27
2.2.3 微弧氧化之鍍層結構及性質 31
2.2.4 微弧氧化電解液之選用 33
2.2.5 微弧氧化法應用於不同基材之比較 36
2.3 以微弧氧化法在鎂合金上鍍製鋯酸氧化膜 42
2.3.1 氧化鋯結構及特性 43
2.3.2 微弧氧化電解液中添加氧化鋯顆粒 46
2.3.3 微弧氧化電解液中添加鋯酸鹽類 50
第三章 實驗方法與步驟 56
3.1 試片材料及製備 56
3.2 微弧氧化程序 58
3.2.1 實驗設備 58
3.2.2 微弧氧化實驗參數 59
3.3微弧氧化鍍膜性質分析原理 62
3.3.1 電子顯微鏡與元素能譜分析 63
3.3.2 X光繞射儀 (X-ray Diffractometer) 64
3.3.3 維氏硬度 65
3.3.4 極化曲線測試(Potentio-dynamic polarization Test) 66
3.3.5 浸泡測試(Immersion test) 69
第四章 結果與討論 70
4.1 以微弧氧化法於AZ91D鎂合金上鍍製矽酸鹽類氧化膜 70
4.1.1 矽酸鹽電解液系統鍍膜之電流影響 71
4.1.2 矽酸鹽電解液系統鍍膜之電解液性質比較 74
4.1.3 矽酸鹽電解液系統鍍膜之微觀結構分析 77
4.1.4 矽酸鹽電解液系統鍍膜之厚度分析 90
4.1.5 矽酸鹽電解液系統鍍膜之成份結構分析 92
4.1.6 矽酸鹽電解液系統鍍膜之硬度表現 94
4.1.7 矽酸鹽電解液系統鍍膜之耐蝕表現 96
4.2 以微弧氧化法於AZ91D鎂合金上鍍製鋯酸鹽類氧化膜 99
4.2.1 鋯酸鹽電解液系統鍍膜之電流影響 100
4.2.2 鋯酸鹽電解液系統鍍膜之電解液性質比較 103
4.2.3 鋯酸鹽電解液系統鍍膜之微觀結構分析 106
4.2.4 鋯酸鹽電解液系統鍍膜之厚度分析 119
4.2.5 鋯酸鹽電解液系統鍍膜之成份結構分析 121
4.2.6 鋯酸鹽電解液系統鍍膜之硬度表現 123
4.2.7 鋯酸鹽電解液系統鍍膜之耐蝕表現 125
4.3 矽酸鹽及鋯酸鹽類系統氧化膜腐蝕行為及耐蝕表現 128
4.3.1 浸泡測試 128
4.3.2 不同浸泡時間之極化曲線分析 130
4.3.3 不同時間浸泡後氧化膜之腐蝕行為分析 134
第五章 結論 141
參考文獻 143

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