為了解決金屬玻璃的變形限制，最近幾年開發新的三元或四元合金系統在非晶態基地相內生成二次相，這些系統在非晶質基地相內有二次相顆粒或是奈米結晶、相分離區域和各種集群的短程有序結構。根據玻璃形成能力，可生成非晶/非晶、非晶/短程有序或是非晶/結晶的複合結構。研究新型複合結構或許能夠改善塊狀金屬玻璃的延展性，意即非晶/結晶或是非晶/短程有序的複合材料取代非晶/非晶複合材料。
根據熱力學計算法，本研究在Zr-Cu-Ni-Al相分離系統內提出一個Zr基新合金（Zr63.36Cu17.22Ni11.47Al7.95），並在不同冷卻速率下描述其微觀組織和晶體結構。依冷卻速率快至慢可得到完全非晶態結構、非晶態/短程有序與非晶態/結晶的複合結構，雖然實驗結果沒有如預期般產生相分離現象，但是意外形成短程有序結構液滴相與非晶態結構基地相的雙相複合結構。令人感興趣的是液滴相與非晶態基地相的平均組成只有實驗上的誤差值，表示凝固的過程中，沒有局部的初晶相成核成長發生，使得液滴相與非晶態基地相成份組成一樣。
為了解組成成分相同卻有不同的影像對比，使用XRD、EBSD與TEM分析是否為不同程度的有序結構所引起，結果得知液滴相中存在三種不同的短程有序結構，貢獻微弱的結晶訊號，與非晶態基地相有著結構上差異。最後使用熱處理方式了解液滴相和基地相與平衡相之間的關係，結果得知Cubic結構Zr2Ni(Al,Cu)-type相是一介穩態結晶相，在本研究的實驗溫度686 K下會發生相變態；高溫穩定相之一的Tetragonal結構Zr2Cu(Al,Ni)-type相，與Zr-Cu-Ni三元系合金800℃平衡相圖的結果相符合。

To solve the problem of limited deformation in metallic glass, newly ternary or quaternary alloy systems have developed the second phase within an amorphous matrix in recent years. These alloy systems have second-phase particles or nanocrystals in a glassy matrix, phase-separated regions, and variations in short-range order by clustering. The second phase within an amorphous matrix can produce the amorphous/amorphous, amorphous/short-range order or amorphous/crystalline composite structure, depending on its glass-forming ability (GFA). Investigating the possibility for the design of a new type of composite structure (i.e., amorphous/crystalline or amorphous/short-range order composites instead of amorphous/amorphous composites) may be able to improve the ductility of BMG.
This study presents a newly designed Zr-based alloy (Zr63.36Cu17.22Ni11.47Al7.95) in Zr-Cu-Ni-Al phase separation system based on thermodynamic-computation approach, and describes its microstructure and crystal structure with different cooling rates. It can obtain completely amorphous structure, the amorphous/ short-range order and the amorphous/ crystalline composite structure by fast to slow cooling rate. Although the experimental result was no phase separation phenomenon as expected, but it was surprisingly that forming the dual phase composite structure with short-range order droplet phase and amorphous matrix phase. And it was interesting that the average compositions of the droplet-type phase and amorphous matrix phase were identical within experimental error. It means that no local primary nucleation and growth was occurring during solidification process, so that the compositions of droplet phase are the same as the compositions of matrix amorphous phase.
In order to understand the same chemical composition but have different image contrast, that we use XRD, EBSD and TEM analysis to understand whether they caused by different degrees ordered structure. The results show that there are three different short-range order structures in droplet-type phase. Therefore, it contributes to the weak crystallization signals and the structure is different from the amorphous matrix phase. Finally, we use the heat treatment in order to understand the relationship between the droplet phase, the matrix phase and equilibrium phase. The results show that the Zr2Ni(Al,Cu)-type phase of cubic structure is a metastable phase and it will occur phase transformation at 686 K in the present study. The Zr2Cu(Al,Ni)-type phase with high temperature stability match the result of phase equilibrium in the Zr-Cu-Ni System at 800℃.

論文審定書.......................................................................................................................... i
致謝.................................................................................................................................... ii
中文摘要............................................................................................................................ iii
英文摘要............................................................................................................................ iv
總目錄................................................................................................................................ vi
圖目錄.............................................................................................................................. viii
表目錄................................................................................................................................ xi
第一章 前言................................................01
第二章 文獻回顧..........................................03
2.1非晶質合金概述.......................................03
2.2非晶質合金之製造方法.............................03
2.3非晶質熱力學性質....................................04
2.3.1 玻璃轉換溫度Tg....................................04
2.3.2 過冷液相區ΔTx.....................................05
2.3.3 簡化玻璃溫度Trg...................................06
2.3.4 γ和γm指數...........................................06
2.3.5非晶質合金的成型能力............................07
2.4金屬玻璃相分離.........................................08
2.4.1相分離簡介.............................................08
2.4.2相分離熱力學條件...................................09
2.5雙相非晶質合金製備方式............................12
2.5.1旋鑄融煉法.............................................12
2.5.2固化成型法.............................................14
2.5.3機械合金法.............................................14
2.6平衡相圖...................................................15
2.6.1 Zr-Cu-Ni與Zr-Cu-Ni-Al合金平衡相圖..........16
2.7背向散射電子繞射簡介................................16
第三章 實驗步驟.............................................42
3.1合金試片配製.............................................42
3.2試片製備方式.............................................43
3.3熱分析量測................................................44
3.4 EPMA量測分析.........................................44
3.5 XRD量測分析............................................45
3.6 TEM量測分析............................................45
3.7 EBSD量測分析..........................................45
3.8硬度量測量測分析.......................................46
第四章 結果與討論...........................................51
4.1合金設計.....................................................51
4.2 EPMA分析結果...........................................51
4.3熱性質分析結果............................................53
4.4硬度分析結果...............................................54
4.5 XRD分析結果..............................................54
4.6 EBSD分析結果............................................56
4.7 TEM分析結果..............................................57
4.8熱處理.........................................................59
第五章 結論......................................................87
第六章 參考文獻 ...............................................89

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