CuZrAl、CuZrAl-V與CuZrAl-Co合金經由吸鑄鑄造成金屬玻璃複合材料。首先Cu50Zr43Al7金屬玻璃由能量釋放的角度分析其應力¬¬ 應變曲線下的鋸齒狀特徵以及破斷面與剪切帶之間的關連。為了鑄造微米尺度第二相之金屬玻璃複合材料，添加3至10原子百分比釩或鈷至CuZrAl合金中經由吸鑄法鑄造並分析其微結構以及機械性質。經由過飽和析出之富釩相形成尖銳尖端樹枝狀結構，導至應力集中並且降低了機械性質。另一方面，由於液態分離而形成的圓形富鈷相，由於其較低的應力集中現象而使機械性質得以提高或是維持。同時，添加1原子百分比之釩至CuZrAl合金中誘導了奈米尺度的B2-CuZr相，由研究發現少量添加釩之後，促使形成B2-CuZr相並提高了機械性質，並經由剪切帶增加、耗損能量、攣晶、應變誘導相變化以及晶粒粗化等不同的觀點分析其機械性質提升之機制。
由研究結果以及文獻參考發現，晶粒大小可能決定了應變誘導麻田散鐵相變化或是攣晶的發生與否，而晶粒大小與製程中所使用的模具吸鑄口的形貌有著相當大的關連，這項研究的最終任務是檢視尖銳或士鈍口模具對於鑄造後B2-CuZr相的大小以及金屬玻璃複合材料的機械性質之間的關係。由研究結果發現，當B2-CuZr相的大小大於關鍵尺寸後，會誘導形成麻田散鐵相變化或是攣晶，並且基於流體力學的理論建構出一個分析模型，經由與實驗結果的印證，發現模型與實驗之間的對照是十分令人滿意的。

CuZrAl and CuZrAl-V and CuZrAl-Co amorphous alloys were cast by rapid suction casting. Flow serrations and fracture morphologies of the base monolithic Cu50Zr43Al7 bulk metallic glasses (BMGs) are first studied by compression at a low strain rate and analyzed by an energy release perspective.
Vanadium or cobalt from 3 to 10 at% is alloyed to the amorphous CuZrAl base alloys to induce precipitation in order to form the bulk metallic glass composites (BMGCs) with micro-sized second phase domains. The V-rich second phase formed during rapid cooling possesses a sharp dendrite shape, inducing stress concentration in the amorphous matrix and lowering the mechanical performance. The Co-rich phase, formed from liquid phase separation, possesses round morphology, lowering the stress concentration and raising or sustaining the mechanical properties.
Meanwhile, 1 at% vanadium was alloyed to the amorphous CuZrAl base alloy to induce nano-sized B2-CuZr phase formation in order to improve compressive plasticity. It was found that the dilute vanadium addition induced B2-CuZr formation and, thus, improved plasticity of the CuZrAl alloy. The role of vanadium on plasticity improvement was discussed in the frame of shear band multiplication, energy dissipation during shear banding, twinning/phase transformation of the B2-CuZr particles during deformation, and deformation induced B2-CuZr particle coarsening.
It was suggested that such transformation induced plasticity would show dependence on the B2 particle size, which in-turn depends on the inlet shape of the suction casting mold in use. It follows that the final task of this research was to examine the effects of the B2 size and distribution, resulted from the sharp or blunt inlet mold, on the mechanical plasticity in the CuZrAl and CuZrAlCo BMGs and BMGCs. It appears that the B2 particles need to be over some critical size to induce the martensitic/twinning transformation into the B19’ phase (sometimes with twins embedded). An analytic model, based on melt flow dynamics with or without vena contraction, is established, and the agreement between experiment and model is satisfactory.

論文審定書 i
誌謝 ii
摘要 iv
Abstract v
Content vii
List of Tables x
List of Figures xii
Chapter 1 Introduction 1
1.1 Amorphous alloys 1
1.2 Bulk metallic glasses 2
1.3 Motivation 4
Chapter 2 Background 8
2.1 The history of amorphous alloys 8
2.2 The fabrication methods of amorphous alloys 11
2.3 The forming condition of amorphous alloys 12
2.3.1 The glass forming ability 12
2.3.2 Empirical rules for the formation of amorphous alloys 17
2.4 Characterization of amorphous alloys 22
2.4.1 Mechanical properties 23
2.4.2 Magnetic properties 25
2.4.3 Chemical properties 25
2.4.4 Other properties 26
2.5 Mechanical behaviors of amorphous alloys 27
2.5.1 Stress-strain curves and fracture morphologies 27
2.5.2 Temperature effect 28
2.5.3 Strain rate effect 31
2.5.4 Sample size effect 32
2.5.5 Geometric constraint effect 33
2.5.6 Deformation mechanisms of metallic glasses 35
2.6 Strategies to improve mechanical properties of metallic glasses 37
2.7 The development of Cu-based metallic glasses 40
2.8 Deformation induced martensitic transformation of CuZr B2 phase 41
Chapter 3 Experimental procedures 43
3.1 Raw materials 43
3.2 Computational thermodynamic approach 43
3.3 Sample preparations 45
3.3.1 Arc melting 45
3.3.2 Suction casting 46
3.3.3 Suction casting with different inlet edged molds 47
3.4 Identifications of amorphous nature 48
3.4.1 X-ray diffraction analyses 48
3.4.2 Thermal analyses 48
3.4.3 Qualitative and quantitative analyses 49
3.5 Mechanical tests 49
3.5.1 Sample preparation 49
3.5.2 Compression test 50
3.6 SEM observations 51
3.7 TEM observations 51
Chapter 4 Results 52
4.1 Sample observations 52
4.2 Monolithic bulk metallic glasses 52
4.2.1 XRD and SEM/EDS analyses 52
4.2.2 Mechanical properties 53
4.2.3 Fracture surface observations 53
4.3 BMGCs with micro-sized second phases 54
4.3.1 Microstructure analyses 55
4.3.2 Mechanical properties 57
4.4 BMGCs with nano-sized second phases 58
4.4.1 Microstructure analyses 58
4.4.2 Mechanical properties 59
4.5 BMGCs cast by two different molds 60
4.5.1 Microstructure analyses 60
4.5.2 Mechanical properties 62
Chapter 5 Discussion 63
5.1 Flow serrations of monolithic BMGs from energy release perspective 63
5.2 Mechanical response of micro-scaled phases in CuZrAl-V/Co BMGCs 67
5.3 Effects of V on phase formation and plasticity improvement 70
5.4 Effect of cast mold inlet orifice on plasticity of Cu-Zr-Al glassy alloys 76
5.5 Effects of B2 size on martensitic/twinning transformation and mechanical plasticity 82
Chapter 6 Conclusion 83
References 86
Tables 97
Figures 110

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