低玻璃轉換溫度之非鐵基塊狀金屬玻璃之研究

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研究生：	王碩宏 Wang, Shuo-Hong
論文名稱：	低玻璃轉換溫度之非鐵基塊狀金屬玻璃之研究 Exploration of non-ferrous bulk metallic glasses with low glass transition temperature
指導教授：	金重勳 Chin, Tsung-Shune
口試委員:	謝克昌葉均蔚李丕耀鄭憲清
學位類別：	博士 Doctor
系所名稱：	工學院 - 材料科學工程學系 Materials Science and Engineering
論文出版年：	2012
畢業學年度：	100
語文別：	英文
論文頁數：	124
中文關鍵詞：	低玻璃轉化溫度、塊狀金屬玻璃、金基、鈣基、熱機械性質、黏度、腐蝕、空氣電池
外文關鍵詞：	Low glass transition temperature, Bulk metallic glass, Au-based, Ca-based, Thermomechanical property, Vuscosity, Corrosion, Air battery
相關次數：	點閱：2 下載：0
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近來在成本效益的考量下，可預期具有低玻璃轉換溫度及低成本之塊狀金屬玻璃將可提升其應用上的價值。本研究主要在於開發新式金基及鈣基塊狀金屬玻璃，與研究其熱機械性質及探討微量添加元素之影響，並試圖找出新的應用。對於具有低玻璃轉換溫度的四元金基塊狀金屬玻璃而言，Sn被用來降低Au的含量以提升其成本效益。此塊狀金屬玻璃之有效黏度範圍為1E8 − 1E9 Pa.s。而其最低黏度值約落在100 °C，這將使得此塊狀金屬玻璃能在沸水中便易於加工變形。因此，此塊狀金屬玻璃將可被應用於奈米壓印，奈米微機電系統，珠寶首飾，及牙科補綴材料。再者，對於同樣具有低玻璃轉換溫度的鈣基塊狀金屬玻璃而言，因組成成分所需成本較低，故屬於具有成本效益之塊狀金屬玻璃。Li的微量添加除了可降低Ca65Mg15Zn20塊狀金屬玻璃本身之玻璃轉換溫度之外，並無太大的效用，卻反而會增加Ca65Mg15Zn20塊狀金屬玻璃之黏度。故Ca65Mg15Zn20 和 (Ca65Mg15Zn20)95Li5塊狀金屬玻璃之有效黏度範圍為1E7 − 1E8 Pa.s。至於(Ca65Mg15Zn20)95Al5 和 (Ca65Mg15Zn20)95Cu5塊狀金屬玻璃之有效黏度則較低，在1E7 Pa.s的範圍之內。其中，(Ca65Mg15Zn20)95Al5塊狀金屬玻璃具有最低的黏滯活化能(1.8 eV)及最大的形變量，以證明其具有最佳的可加工形變能力。
為了將鈣基塊狀金屬玻璃應用於空氣電池，所以使用一簡單的三元Ca65Mg15Zn20塊狀金屬玻璃以清楚瞭解其在氫氧化鉀溶液中之電化學性質。藉由陽極極化量測分析可以知道，在高濃度的氫氧化鉀電解液中，Ca65Mg15Zn20塊狀金屬玻璃可觀察到最低腐蝕電流密度為63(1E6) A/cm2，以及相對應的最慢腐蝕速率為2 mm/year。較高的腐蝕電位意味著較易形成鈍化層而產生抗腐蝕的保護作用。對於這些特殊的腐蝕行為而言，鈍化層為非常重要的抗腐蝕關鍵。而表面分析的結果說明鈍化層主要是由氫氧化鈣，氫氧化鎂，氫氧化鋅所組成。經由放電測試提供了鈣基塊狀金屬玻璃應用於空氣電池的初步結果，發現其於稀KOH中表現較佳，與傳統鋅空電池不同。相信此研究除了拓展鈣基塊狀金屬玻璃之應用面外，也將使得塊狀金屬玻璃未來於空氣電池之應用開啟一扇門戶。

Abstract                                               I
Abstract (in Chinese)                                 II
Acknowledgement                                      III
List of Tables                                        IX
List of Figures                                        X

--------------------------------------------------------
Chapter 1 Background and Motivation                    1
1-1 An introduction to metallic glasses                1
1-1-1 Metallic glasses as new functional materials     1
1-1-2 A glance at non-ferrous metallic glasses         2
1-2 Purposes of this study                             4

Chapter 2 Literature Review                            6
2-1 History of metallic glasses                        6
2-2-1 Non-ferrous bulk metallic glasses                9
2-1-1-1 Non-ferrous bulk metallic glasses with high Tg 9
2-1-1-2 Non-ferrous bulk metallic glasses with low Tg 12
2-2-2 Ferrous bulk metallic glasses                   17
2-2 Characterization of metallic glasses              18
2-2-1 Mechanical properties and applications          18
2-2-2 Electrical properties                           21
2-2-3 Electrochemical properties and applications     21
2-2-4 Thermo-mechanical properties and applications   23
2-2-5 Magnetic properties and applications            25
2-3 Methods to fabricate metallic glasses             26
2-4 Empirical rules for alloys with better GFA        27
2-5 Criteria for indicating the glass forming ability 28
2-6 Properties and requirements of an air-battery     31

Chapter 3 Experimental Procedures                     34
3-1 Working flow chart                                34
3-2 Sample preparation                                35
3-2-1 Arc-melting technique of Au-based BMG           35
3-2-2 Copper mold casting of Au-based BMG             36
3-2-3 Copper mold pour-casting of Ca-based BMG        36
3-3 Analyses of structure and thermal properties      38
3-3-1 X-ray diffractometer (XRD)                      38
3-3-2 Transmission electron microscope (TEM)          39
3-3-3 Differential thermal analyzer (DTA)             40
3-4 Analyses of electrochemical properties            42
3-4-1 Polarization analyzer (Tafel)                   42
3-4-2 Cyclic voltammeter (CV)                         44
3-4-3 Discharge tester                                45
3-5 Analyses of thermal mechanical properties         46
3-5-1 Thermal mechanical analyzer (TMA)               46
3-6 Analyses of passive layer on the surface          48
3-6-1 Raman spectrometer (Raman)                      48
3-6-2 Fourier-transform infrared spectrometer (FTIR)  49

Chapter 4 Exploration of Au-based BMG Systems         51
-Deformation capability of new quaternary Au-Sn-Cu-Si BMG systems-                                              51
4-1 Motivation                                        51
4-2 Experimental procedures                           53
4-3 Results and Discussion                            54
4-3-1 Structure examination                           54
4-3-2 Thermal analyses                                55
4-3-3 Thermal mechanical analyses                     57
4-3-4 Estimation of viscosity                         59
4-3-5 Observation of deformation capability           61
4-4 Summary                                           63

Chapter 5 Exploration of Ca-based BMG Systems         64
5-1 Deformation capability of Ca65Mg15Zn20 and Ca-Mg-Zn-(Li, Al, Cu) BMG systems                                   64
5-1-1 Motivation                                      64
5-1-2 Experimental procedures                         66
5-1-3 Results and Discussion                          67
5-1-3-1 Structure examination                         67
5-1-3-2 Thermal analyses                              68
5-1-3-3 Thermal mechanical analyses                   70
5-1-3-4 Estimation of viscosity                       77
5-1-3-5 Activation energy of viscous deformation      81
5-1-4 Summary                                         86
5-2 Corrosion behaviors and application of Ca65Mg15Zn20 BMG 
                                                      88
5-2-1 Motivation                                      88
5-2-2 Experimental procedures                         90
5-2-3 Results and Discussion                          91
5-2-3-1 Structure examination and Thermal analyses    91
5-2-3-2 Electrochemistry analyses                     92
(1) Polarization test (Tafel)                         92
(2) Cyclic voltammetry (CV)                           95
5-2-3-3 Schematic model of corrosion behaviors        96
5-2-3-4 Surface analyses                              98
(1) XRD analysis                                      98
(2) SEM observation                                   99
(3) Raman analysis                                   101
(4) FTIR analysis                                    101
5-2-3-5 Application to an air battery                103
5-2-4 Summary                                        105

Chapter 6 Concluding Remarks and Prospects           106
6-1 Conclusions of this study                        106
6-1-1 Au-based BMG                                   106
6-1-2 Ca65Mg15Zn20 BMG                               107
6-1-3 Novel Ca-based BMG systems                     109
6-2 Suggested future works                           111

References                                           113
Publication List                                     120
Appendix-Other Research on Pb-free Solders           122



                                

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