本研究的目的為針對耐火高熵合金的強化機制做更深入的探討，並針對應用進行新合金開發。第一部分利用固溶強化效應的理論計算，探討耐火金屬元素對耐火高熵合金機械性質的影響。第二部分利用第一部分的固溶強化的理論計算，搭配混合法則計算熔點來設計合金，並利用超高溫熱處理爐進行均質化，得到擁有良好高溫強度的單相 BCC 無序固溶體的耐火高熵合金，該合金在 1600℃ 下擁有 571 MPa 的高溫壓縮強度，打破目前耐火高熵合金的最高紀錄，同時透過該合金檢討固溶強化理論不足之處，提出 critical temperature 以及 plateau strength 的原理。第三部分為針對核融合反應器中的 plasma-facing material 所需要的特性，包含高熔點、高硬度、良好高溫強度、耐離子沖蝕的應用，設計耐火高熵 Laves phase 合金，這種合金是以 Laves phase 為主體，超越了目前 BCC + Laves phase 耐火高熵合金的高溫強度，因而提供了一個新的合金設計方向。第四部分則設計了一款可以利用熱機處理成單相，並且可在中溫析出的輕量化耐火中熵合金，該合金以鈦為主，可在室溫滾壓，且可進行高溫拉伸，具有低密度以及耐一定氧化的特性，與雙相比較，耐火高熵合金單相機械性值優越，其原因也進行探討。

This research was focus on the development and application on refractory high-entropy alloys (RHEAs). In the first part, the solid-solution strengthening calculation was applied on the several RHEAs to understand the refractory elemental effects of RHEAs on mechanical properties. In the second part, the solid-solution strengthening calculation and the melting point estimated by rule of mixing were used to design a new RHEA system. The homogenization treatment conducted by Ultra-high temperature furnace was applied on the alloys to get the disorder BCC solid-solution phase. One of the alloys possesses the elevated-temperature strength 571 MPa at 1600℃, which is the best record of RHEAs. Also, the assumption of the solid-solution strengthening calculation was re-discussed, and the critical temperature and the plateau strength properties of this kind of RHEAs were studied in depth. In the third part, the refractory high-entropy Laves phase alloys were design for plasma-facing material application in fusion reactors. These alloys possess Laves phase matrix for high melting point, high hardness, and good elevated-temperature strength with minor BCC phase for toughness. The refractory high-entropy Laves phase alloys have better elevated-temperature strength than published BCC +Laves phase RHEAs, and provide a new way to design RHEAs. In the fourth part, the reason why RHEAs with only one phase are better than the RHEAs with dual phase was studied. A refractory medium-entropy alloy was design and could have only one BCC phase or BCC + Laves phase by different thermal-mechanical treatments. During the experiments, the reason why RHEAs with only one phase are better than the RHEAs was found.

致謝 I
摘要 IV
Abstract V
目錄 VII
圖目錄 XII
表目錄 XXIII
壹、 前言 1
貳、 文獻回顧 4
2.1 高熵合金 (High-entropy alloys) 4
2.1.1 高熵合金之定義 7
2.1.2 高熵效應 (High-entropy effect) 7
2.1.3 嚴重晶格扭曲效應 (Severe-lattice-distortion effect) 10
2.1.4 遲緩擴散效應(Sluggish diffusion effect) 13
2.1.5 雞尾酒效應(Cocktail effect) 15
2.1.6 高熵合金的相預測計算 16
2.2 耐火高熵合金 19
2.2.1 MoNbTaW 與 MoNbTaVW [40, 46] 21
2.2.2 HfNbTaTiZr [41, 42] 23
2.2.3 鉻添加耐火高熵合金 25
2.2.4 鋁添加耐火高熵合金 28
2.2.5 輕量化耐火高熵合金 30
2.2.6 高延展性耐火高熵合金 30
2.2.7 綜合討論 34
2.3 核能反應器 37
2.3.1 核反應 39
2.3.2 中子截面 (Neutron cross section) 41
2.3.3 放射性與衰變 48
2.3.4 爐心組成要素 [70] 51
2.3.5 輕水式反應器 (Light water reactor) 54
2.3.6 快中子滋生反應器 (Fast breeder reactor) 57
2.3.7 第四代核反應器 [71] 58
2.3.8 核融合反應器 64
2.4 輻射損傷與輻射效應 67
2.4.1 輻射損傷 67
2.4.2 輻射效應 71
2.5 核能結構材料 76
2.5.1 肥力鐵型/麻田散鐵型不鏽鋼 79
2.5.2 奧斯田鐵型不鏽鋼 79
2.5.3 鎳基超合金 82
2.5.4 氧化物散佈強化鋼 82
2.5.5 耐火合金 82
2.5.6 高熵合金在輻射損傷研究的現況 84
參、 實驗方法 89
3.1 真空電弧熔煉 89
3.2 滾壓 89
3.3 硬度量測 90
3.4 室溫壓縮 90
3.5 高溫壓縮 90
3.6 室溫拉伸 91
3.7 高溫拉伸 91
3.8 超高溫熱處理 92
3.9 真空石英封管 93
3.10 蝕刻 93
3.11 微結構觀測 94
3.12 晶體結構分析 94
3.13 相分率量測 94
肆、 實驗結果與討論 95
4.1 耐火高熵合金的固溶強化效應 [90] 95
4.1.1 耐火高熵合金的固溶強化模型 95
4.1.2 Hf-Mo-Nb-Ta-Ti-Zr 系列耐火高熵合金的固溶強化效應計算 98
4.2 高溫強度超越 MoNbTaVW 的耐火高熵合金開發 102
4.2.1 合金設計 102
4.2.2 微結構 106
4.2.3 機械性質 110
4.2.4 模型參數修正討論 116
4.3開發應用於 plasma-facing material 的耐火高熵合金 122
4.3.1 等莫耳耐火高熵 Laves phase 合金 122
4.3.2 等莫耳耐火高熵 Laves phase 合金微結構及機械性質 123
4.3.3 非等莫耳耐火高熵 Laves phase 合金 131
4.3.4 非等莫耳耐火高熵 Laves phase 合金微結構及機械性質 135
4.3.5 討論 145
4.4 低密度析出型耐火中熵合金熱機處理研究 149
4.4.1 合金設計 149
4.4.2 微結構 153
4.4.3 機械性質 172
4.4.4 析出強化討論 180
伍、 結論 183
陸、 重要貢獻 186
柒、 未來研究方向 188
捌、 著作列表 189
7.1 國際論文發表 (依照作者序排序) 189
7.2 國際研討會發表 (依照時間序排序) 191
玖、 參考資料 192

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