中文摘要
本研究以等徑轉角擠形(Equal Channel Angular Pressing, ECAP)擠製，路徑為BA、擠製次數12次之ZK60合金(Mg-5.7Zn-0.5Zr ,wt%)，以機械取屑並添加5C及不同比例的Ag、Al及Co元素進行球磨20小時所製備的儲氫粉末，探討其儲氫性質。實驗結果顯示，添加0.5Ag、0.1Al、0.3Co為最佳比例有最好的吸氫量，其吸氫量分別為 7.1wt%、6.7wt%、6.8wt%。探討合金高週期循環特性時，固定添加5C及不同比例的Pd、Pt、Ag及Fe、Co、Al，進行循環試驗以分析其吸放氫循環特性。實驗結果顯示，添加0.5Pd循環效果最好，經500次循環後吸氫量遞減20.6%，其次是添加0.7Pt與0.5Ag，經500次循環後吸氫量遞減27.7%與29.1%。其中添加0.5Pd與0.5Ag從第50次至500次之循環，共經450次循環之吸氫量只再遞減3.0%及0.5%，顯示對高週期之循環吸放氫性能非常良好；而添加0.7Pt吸氫量之遞減未有明顯減緩之趨勢，顯示添加0.7Pt對循環吸放氫性能相對不佳。添加0.5Fe、0.3Co、0.3Al與上述結果比起來相對較差，添加0.5Fe，經300次循環吸氫量遞減39.7%，其次是添加0.3Co與0.3Al，分別經250次與150次循環吸放氫後遞減39.7%及40.9%。關於高週期循環之吸氫速率，添加Al、Fe、Co、Pt均能有效提升高週期之吸氫速率，添加Pd及Ag並沒有明顯影響其吸氫速率。
經ECAP BA 12次之ZK60合金會產生奈米晶粒，晶粒大小約為41.9 nm，經過400℃持溫10小時並不會產生明顯之晶粒成長，顯示其熱穩定性非常良好；但溫度提升到450℃持溫10小時，將會產生顯著之晶粒成長，晶粒明顯長大至約70.6 nm；若經500℃10小時之熱處理合金將會熔坍。

Abstract
The ZK60 (Mg-5.7Zn-0.5Zr,wt%) alloy was refined by equal channel angular pressing (ECAP) with route B¬A and 12 passes. The alloy became metal filings by mechaneal method and the metal powders were prepared by adding 5wt% carbon and various amounts of Silver, Aluminum and Cobalt in ball milling for 20hrs.Then the hydrogen storage capacity of the ZK60 alloy was investigated. Experimental results showed that the alloys with adding 0.5Ag, 0.1Al and 0.3Co have the best hydrogen storage capacity which are 7.1wt%, 6.7wt% and 6.8wt%, respectively. The characteristics of the alloys under high cycling were investigated, with adding 5C and various amounts of Palladium,Platinum, Silver , Iron, Aluminum, and Cobalt. Experimental results showed that the best performance of the alloys under high cycling is obtained by adding 0.5Pd, and after 500 cycles the hydrogen storage capacity decreases 20.6%. It is followed by adding 0.7Pt and 0.5Ag, with the hydrogen storage capacity decrease of 27.7% and 29.1%, respectively, after 500 cycles. Note that the hydrogen storage capacity just only decreases 3.0% and 0.5% for the alloys with adding 0.5Pd and 0.5Ag in the duriation between 50th and 500th cycles. It shows that the high cycling performance of the alloys with 0.5Pd and 0.5Ag is very well. While for the alloy with adding 0.7Pt, the hydrogen storage capacity still decreases obviously with increasing the cycling number, showing relatively poor performance. For the alloys with adding 0.5Fe, 0.3Co, 0.3Al, the high cycling performance is relatively poor as compared with the above results. The hydrogen storage capacity decreases 39.7% for the alloy with 0.5 Fe after 300 cycles, and it decreases 39.7% and 40.9% for the alloys with 0.3Co and 0.3Al after 250 and 150 cycles, respectively. The hydrogen absorption rate of the alloys under high cycling can be effectively enhanced by adding Al, Fe, Co, Pt. However, it does not be significantly affected by adding Ag and Pd.
After ECAP with route BA and 12 passes, the nanocrystalline microstructure of the alloys can be formed, with grain sizes about 41.9 nm. After 400℃/10 hours heat treatment, the grain sizes nearly unchange, showing the excellent thermal stability of the alloys. When increasing the temperature to 450℃ and still holding for 10 hours, the alloys are thermally unstable, with the grain growth to 70.6 nm. Under 500℃/10 hours heat treatment, the alloys will be remolten and collapsed.

總目錄
中文摘要 I
Abstract III
總目錄 V
圖目錄 IX
表目錄 XIII
第一章前言 1
第二章文獻回顧 4
2.1氫的介紹 4
2.1.1 氫的基本性質 4
2.1.2 氫的燃燒 6
2.2氫的儲存 8
2.2.1 高壓氫氣儲氫 9
2.2.2 液態氫氣儲氫 10
2.2.3 金屬氫化物儲氫 11
2.2.4 化學氫化物儲氫 11
2.2.5 有機化合物儲氫 12
2.2.6 其他儲氫材料 14
2.3儲氫合金 15
2.3.1 儲氫合金簡介 15
2.3.2 儲氫合金的優缺點 17
2.3.3 儲氫合金類型 17
2.3.3.1 AB型 (Ti-Fe系) 18
2.3.3.2 A2B型 (Mg系) 19
2.3.3.3 AB2型 (Laves相系) 20
2.3.3.4 AB5型(稀土系) 21
2.4 儲氫合金吸放氫動力學 22
2.5 儲氫合金熱力學 26
2.6 等徑轉角擠形(Equal Channel Angular Pressing, ECAP) 30
2.6.1 等徑轉角擠形之應變 33
2.6.2 等徑轉角擠形之路徑 33
2.6.3 等徑轉角擠形對ZK60儲氫性能之影響 38
2.7 機械合金(Mechanical Alloying, MA) 39
2.7.1 機械合金法之原理 39
2.7.2 球磨機種類 40
2.7.3 球磨速度與時間 41
2.7.4 鋼球與粉體之重量比(球粉比) 41
2.7.5 球磨氣氛 41
2.7.6 球磨溫度 42
2.8 鎂合金簡介 42
2.8.1 添加元素對鎂合金元素的影響 43
2.8.2 鍛造鎂合金晶粒細化及性能 46
2.9 奈米晶粒的熱學基本性質【62】 48
2.9.1 熱學基本性質 48
2.9.2 奈米晶粒的熱穩定性 49
第三章 實驗步驟與方法 52
3.1 實驗流程圖 53
3.2 合金粉末製備 54
3.2.1 等徑轉角擠形與機械取屑 54
3.2.2 合金粉末製備 56
3.3合金儲氫性質檢測 57
3.3.1 活化 59
3.3.2 動力學曲線 60
3.4實驗設備 60
3.4.1 ICP-AES成分分析 60
3.4.2 X-ray 繞射分析 61
3.4.3 合金表面形態觀測與EDS 表面分析 61
第四章 結果與討論 62
4.1 ZK60奈米晶粒之熱穩定性 62
4.1.1 顯微組織觀察 63
4.1.2 成分分析 67
4.2 球磨添加物對ZK60 儲氫特性之影響 72
4.2.1添加不同比例之Ag 73
4.2.2添加不同比例之Al 78
4.2.3添加不同比例之Co 83
4.3球磨添加物對高週期循環吸放氫特性之影響 88
4.3.1 Pd、Pt及Ag對循環吸放氫特性之影響 89
4.3.2 Fe、Co及Al對循環吸放氫特性之影響 100
第五章 結論 111
參考文獻 113

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