本研究以真空電弧熔煉爐(Vacuum Arc Remelting,VAR)熔煉配製Fe-25Mn-6Si-5Cr-xZr(x=0.1~0.5)，經熱滾壓至2mm及1150℃固溶處理一小時後水淬，再進行冷滾軋與高溫時效處理，以探討添加Zr對Fe-25Mn-6Si-5Cr合金之形狀記憶性能以及第二相析出行為之影響。
實驗結果顯示，添加Zr後在合金內部會有兩種不同的第二相析出，其一為χ相，晶體結構為體心立方(BCC)，晶格常數為0.89nm，析出溫度介於500℃~800℃之間；其二為含Zr第二相在熱滾軋後即隨機存在合金內部，經過1150℃固溶處理此相依然存在合金內部，此相經過TEM分析其晶體結構為面心立方(FCC)，晶格常數介於0.77~1.16nm。添加Zr對於合金有第二相強化與細晶強化之雙重作用，使得合金在固溶處理狀態下，形狀記憶效應提升了12~13%左右。在固溶處理後直接在500℃~1000℃時效處理一小時，由於Zr第二相的存在使得χ相析出速率變慢且顆粒變小，並能有效阻礙差排移動，使形狀記憶效應在高溫時效後就能達到88.5%；在固溶處理後再經過10%冷滾軋500℃~1000℃退火處理一小時，Zr第二相以及χ相大量規則排列析出在滑移帶上，使得添加0.5Zr之合金形狀記憶效應可高達95.8%。

In this study, Fe-25Mn-6Si-5Cr-xZr(x=0.1~0.5) shape memory alloys were prepared by vacuum arc remelting(VAR). After hot rolling and 1150℃/1hr solution treatment followed by 10% cold rolling and aging treatment, the effects of Zr additives on the shape memory performance and precipitation behavior of the alloys were investigated.
Experimental results showed that there are two kinds of precipitates in the alloys with adding Zr. One is χ phase with body-centered cubic structure and lattice constant 0.89nm. The formation temperature of the χ phase is between 500℃ and 800℃. The other is the precipitate with Zr which exists in the alloys after hot-rolling and is still thermo-stable in the alloys after 1150℃/1hr solution treatment. The crystal structure of the precipitate with Zr is face-centered cubic and its lattice constant is in the range of 0.77~1.17nm. The shape memory performance of the alloys with adding Zr after solution treatment is improved by 12~13%, due to both effects of the second phase and fine-grain strengthening. After 500~1000℃/1hr aging treatment, the formation rate of the χ phase will be slow down and the particle size becames smaller, due to the presence of the precipitate with Zr. It can effectively hinder dislocation motion and the shape recovery ratio can reach 88.5%. After 10% cold rolling and 500~1000℃/1hr annealing treatment, the shape recovery ratio can reach 95.8% by adding 0.5wt% Zr. It is caused by the precipitation of χ phase and precipitate with Zr regularly aligned along the slip bands.

中文摘要...I
ABSTRACT...II
總目錄...IV
圖目錄...VIII
表目錄...XIII
第一章 前言...1
第二章 理論基礎與文獻回顧...4
2.1 形狀記憶合金概述...4
2.2 形狀記憶效應...5
2.2.1 單向記憶效應...6
2.2.2 雙向記憶效應...7
2.2.3 全向記憶效應...8
2.3 鐵基形狀記憶合金之發展沿革...9
2.4 鐵基形狀記憶合金記憶效應基本原理...11
2.5 鐵基形狀記憶合金之相轉變溫度...16
2.5.1 外加應力...16
2.5.2 記憶合金成份之影響...16
2.5.3 冷加工與退火處理...17
2.6 影響FEMNSI基形狀記憶合金效應之因素...21
2.6.1 添加合金元素之影響...21
2.6.2 晶粒大小之影響...27
2.6.3 沃斯成形(ausforming)之影響...27
2.6.4 熱循環...28
2.6.5 變形條件之影響...28
2.6.6 熱機訓練(thermo-mechanical training)之影響...29
2.6.7 熱機處理(thermo-mechanical treatment)之影響...29
2.6.8 析出效應之影響...30
2.7 ZR的特性及應用...35
第三章 實驗方法與流程...38
3.1 合金熔煉與試片製備...38
3.2 熱滾軋...42
3.3 冷滾軋...43
3.4 ICP-OES成分分析...43
3.5 DSC變態溫度量測...45
3.6 金相顯微組織觀察與EDS表面成分分析...46
3.7 穿透式電子顯微鏡(TEM)試片製備與分析...47
3.8 XRD繞射分析...51
3.9 形狀回復率量測...51
3.10 硬度量測...52
第四章 結果與討論...53
4.1 合金基本性質...53
4.1.1 ICP-OES合金成分分析...53
4.1.2 XRD繞射分析...54
4.1.3 DSC相變態溫度量測...59
4.1.4 硬度測試...61
4.2 析出行為觀察分析...62
4.2.1 含Zr之第二相析出過程...62
4.2.2 含Zr之第二相對χ相析出之影響...68
4.2.2.1 固溶處理後直接500℃~1000℃時效處理之觀察...68
4.2.2.2 經10%滾壓後在500℃~1000℃退火處理之觀察...71
4.2.3 含Zr第二相析出物之觀察...75
4.2.3.1 TEM觀察分析...75
4.2.3.2 SEM-EDX成分分析...83
4.3 形狀記憶效應量測...88
4.3.1 時效溫度對合金形狀記憶效應之影響...88
4.3.2 冷滾軋對合金形狀記憶效應之影響...92
第五章 結論...96
參考文獻...98

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