近年來，非晶質合金之未來潛力與實質工業應用開始被多加關注，尤其微機電系統(MEMS)零組件與光電壓印材料方面，更是投注大量的人才來研發。本論文主要以具低玻璃轉位溫度(Tg)之輕量型鎂基非質晶合金，作為新一代的壓印材料之研究。且利用熱機性分析儀(Thermomechanical analyzer)來獲得鎂基非晶質合金之粘度行為與熱機性參數，並進而探討其二次加工性，提出加工溫度區間、耐熱程度等實用之數據，作為日後工業應用之有利資訊。
　　輕量型鎂基非晶質合金具良好之玻璃形成能力(Glass forming ability)，根據鎂基非晶質合金之發展歷程，與熱分析所得之結果，顯示鎂-銅-釔(Mg-Cu-Y)與鎂-銅-釓(Mg-Cu-Gd)之金屬成分是易於製成塊狀鎂基非晶質金屬玻璃(Bulk metallic glass)。本文先以鎂-銅-釔作主軸，藉由熱分析與硬度結果作為依據，獲取最適合之塊狀非晶質合金成分(Mg58Cu31Y11)作為熱壓印材料樣本。樣本經由熱壓印機施予適當應力與時間之下，以幾近完美地形成六角鏡模具，且成功轉印於聚甲基丙烯酸甲酯(Polymethylmethacrylate)之上。有限元素分析法(Finite element simulation)之結果，也與熱機性分析、壓印試片相互印證。
　　此外，鎂-銅-釓之金屬成分更較鎂-銅-釔具良好玻璃形成能力，據相關文獻所言，若以少量銀(Silver)或硼(Boron)元素取代成分鎂-銅-釓(釔)中的銅(Copper)元素原子成分比，將可提升熱穩定性或機械性質，更增加金屬玻璃塊材形成大小，以便加強材料使用性。本論文也探討鎂-銅-(銀，硼)-釓多元鎂基合金之熱機械性質、粘滯流動行為和形變能力等加工性，並利用形變模型來深入探討其內部結構與能量關係之影響。由研究發現，添加銀或硼元素，雖增加塊狀大小、機械性質或熱穩定性，但卻提高粘滯流動困難性、增加活化所需能量、降低形變能力等負面加工性因子，侷限二次形變能力。但銀、硼取代銅元素之玻璃金屬材料確實顯示出較佳之機械性質和室溫下之硬度。由此可知，材料應用性不應只單探討材料之形變能力、熱性質或機械性質，而是需全方面考量其應用所需。
　　最後，本論文提出數個指數如粘滯性(Viscosity)、VFT溫度(Vogel-Fulcher-Tammann temperature)、應力下之熱穩定性、形變性(Deformability)等，以量化數據方式，來得知材料之加工性質，作為塊狀玻璃金屬加工性之參考，以便用於未來應用發展之依據。

In the near couple years, the applications of amorphous alloys have attracted great attention due to their characteristics and future potential. This research is intended to synthesis a lighter Mg-based amorphous alloy as the imprinting materials for micro-electromechanical system (MEMS) with a high glass forming ability (GFA) and lower glass transition temperature (Tg). Also, the workability of the Mg-based metallic glasses is examined in terms of several viscous flow behaviors and parameters obtained from the thermomechanical analysis (TMA).
The lighter Mg-based metallic glasses exhibit their superior glass forming ability, and can be cast into bulk metallic glasses (BMGs). Based on the thermal analysis of the Mg-Cu-Y glassy materials, the evaluation of the glass forming ability and thermal stability for searching the optimum alloy composition is conducted. By using Mg58Cu31Y11 amorphous alloy with the best composition as the micro-forming specimens, imprinting was made by hot pressing at 150oC with several applied compressive stresses to form the hexagonal micro-lens arrays. Finite element simulation using 3D Deform software is also applied to trace the microforming evolution, and to compare with the experimental observations. The results demonstrate that the imprinting is feasible and promising.
On the other hand, the Mg-Cu-Gd BMGs with even better GFA than Mg-Cu-Y are explored in terms of their thermomechanical properties. Extension of this study is performed partially by Cu replacing by Ag or B for the improvement of maximum diameter and thermal stability. And the workability of these Mg-Cu-(Ag, B)-Gd metallic glasses, namely, Mg65Cu25-xAgxGd10 (x = 0, 3, 10 at %) and Mg65Cu22B3Gd10 is evaluated in terming of the thermomechanical parameters, viscous flow behavior, deformability, and the deformation model. It is found the fragility for viscous deformation would increase with the replacement of Ag or B, leading to the negative factors for the micro-forming and nano-imprinting practices. This conclusion is supported by the many extracted parameters.
Thus, even the B-additive Mg based BMG has much higher hardness and Ag-additive Mg based BMG has the larger maximum rod diameter, they are more difficult to be formed, appearing as a negative factor in the micro-forming or nano-imprinting industry. The base Mg65Cu25Gd10 alloy stilly appears to be more promising than the Ag or B-containing alloys when the viscous forming is under consideration.

Table of Content
List of Tables
List of Figures
中文摘要
Abstract
Chapter 1 Introduction
1.1 Glass
1.2 Metallic glasses
1.2.1 Evolution of metallic glasses
1.2.2 Manufacture methods of metallic glasses
1.2.3 Factors of the glass forming ability (GFA)
1.2.4 Bulk metallic glasses
1.2.5 Characterizations of bulk metallic glasses
1.2.6 Application of bulk metallic glasses
1.2.7 Workability of bulk metallic glasses
1.3 Mg-based bulk metallic glasses
Chapter 2 Background and literature review
2.1 The forming conditions of amorphous alloys
2.1.1 The empirical rules for forming amorphous alloys
2.1.2 The correlative theories of empirical rules
2.2 Viscous flow behavior
2.2.1 Thermodynamics and kinetics of metallic glasses
2.2.2 Kinetics and viscosity of metallic glasses
2.2.3 Angell plot and Vogel-Fulcher-Tammann (VFT) formula
2.3 Crystallization of supercooled metallic liquids and glasses
2.4 New viscosity measurement of bulk metallic glasses
2.4.1 Three point beam bending method
2.4.2 Dimensional changes method
2.5 Deformability of supercooled liquids
2.5.1 Deformation behavior
2.5.2 Microforming
2.5.3 Deformability parameter
2.5.4 Deformation model
2.6 Partial element replacement in Mg-Cu-Y(Gd) based bulk metallic glasses
2.6.1 The effect of the boron element
2.6.2 The effect of the silver element
2.7 Purpose of this work
Chapter 3 Materials and Experiments
3.1 The preparation of amorphous alloy specimens
3.1.1 Materials
3.1.2 Arc melting process
3.1.3 Melt spinning technique
3.1.4 Injection casting process
3.2 Microstructure and phase identification
3.2.1 XRD analyses
3.2.2 SEM observations
3.3 Thermal analyses
3.4 Mechanical properties
3.4.1 Hardness
3.4.2 Dynamic mechanical analysis
3.4.3 Thermomechanical analysis
3.5 Imprinting (Micro forming)
Chapter 4 Results and discussions
4.1 The Mg-based amorphous ribbons
4.1.1 Microstructure
4.1.2 Thermal properties
4.1.3 Mechanical analyses
4.2 Thermal and thermomechanical properties of Mg58Cu31Y11 bulk amorphous alloy
4.2.1 Microstructure and thermal properties
4.2.2 Thermomechanical properties
4.2.3 Viscous flow behavior
4.2.4 Deformability
4.2.5 Findings for Mg58Cu31Y11 properties
4.3 Micro-imprinting in Mg-Cu-Y metallic glasses
4.3.1 Finite element simulation
4.3.2 Morphology of the micro-lens mold and imprinted specimens
4.3.3 Comments for micro-imprinting
4.4 Workability and thermomechanical properties of Mg-Cu-(Ag, B)-Gd bulk metallic glasses
4.4.1 Phase demonstration and thermal properties
4.4.2 Thermomechanical analysis
4.4.3 Viscous flow behavior
4.4.4 Mechanical formability
4.4.5 Deformation model
4.4.6 Combined effects of B and Ag addition
Chapter 5 Summary
References
Tables
Figures

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