臺灣博碩士論文加值系統

傳統實用合金系統的開發，主要以Fe、Cu、Al、Mg、Ti和Zr等元素為主。然而，這些合金設計及選擇的理念，仍未脫離以一種元素或化合物為主的觀念。
有鑑於此，本實驗室以無主要元素的多元合金新觀念，設計出等莫耳多元合金，期望能獲得特殊微結構及性質。
本實驗以高溫晶體結構區分為FCC及BCC兩族群，並添加B及Si兩元素作影響評估，共配製十六種等莫耳多元合金。除作微結構觀察、EDX成份分析及X光繞射外，並測試硬度作為機械性質之參考。
研究結果顯示，在FCC多元合金系統中，因為Ag在液態下即對Fe、Co、Ni、Cr排斥，故成為巨觀分相的主因。但Au因不排斥其它元素又能與Ag互溶，因此具有調和的功能，可增加Ag與其它元素的互溶度。但Si的添加會把富Fe、Co、Ni、Cr、Al、Au相中的Au趕走，導致Au僅和Ag、Cu互溶，使Au再度失去調和的功能，液態分相更為明顯。
在BCC多元合金系統中，由於Y和Nd這兩種稀土族元素與其它過渡族金屬元素互溶度甚差，成為巨觀分相的主因。Si不僅與稀土族元素具有良好的固溶度，也與過渡族金屬元素具有良好的固溶度。但是Si並不能有效吸引過渡族金屬元素與稀土族元素聚集在一起，所以雖然Si與兩種族群均有良好的固溶度，仍舊無法抵消兩種族群間的排斥力，以致於巨觀分相情形依舊存在。
在Ni-Co-Fe-Cu-V-Cr-Mo-Au-Ag-Ti-Al-Zr-Y-Nd十四元合金中，FCC及BCC系統易產生分相的Au、Ag、Cu、Y、Nd會聚集在一起，形成富Au、Ag、Cu、Y、Nd之分相，而其餘元素另成一分相。
當Ag、Cu、AuCu、Y、Nd與Mo之分相繞射峰扣除不計後，不論是FCC或BCC多元合金系統，其X光繞射圖的波峰皆簡單許多，容易判別非晶質相的存在。FCC系統的銀色區域為非晶質相，硬度可低至Hv 255（未添加Si）或高至Hv 1007（添加Si）。金色區域為結晶相。BCC系統之黑色區域為富Y或Nd的結晶相，基地相為部分結晶部分非晶質相，其中初晶富Mo相為結晶相，而其餘為非晶質相。其硬度介於Hv 470至Hv 628，含Nd比含Y系統較具軟化作用。
十四元合金的硬度值也出現大幅度的提昇。顯示合金元素越多，原子尺寸差異更大，亂度更高，固溶強化效應越強。

誌謝……………………………………………………………………….I
摘要……………………………………………………………………...II
目錄……………………………………………………………………..IV
圖目錄………………………………………………………………….VII
表目錄………………………………………………………………...XVI
一、 前言……………………………………………………………..1
二、 文獻回顧與理論………………………………………………..3
2.1 非晶質合金發展與應用………………………………….3
2.2 非晶質合金製程………………………………………….5
2.3 非晶質合金優異特性…………………………………….6
2.4 非晶質合金形成理論…………………………………….7
2.4.1 玻璃轉換溫度………………………………….7
2.4.2 孕核與成長………………………………….…9
2.4.3 極限冷卻速率………………………………...10
2.5 影響非晶質合金形成因素……………………………...12
2.5.1 玻璃形成能力………………………………...12
2.5.2 冷卻速率……………………………………...13
2.5.3 合金原子間的鍵結特性與晶體結構特性…...13
2.5.4 約化玻璃轉換溫度…………………………...15
2.5.5 共晶成份……………………………………...15
2.6 等莫耳非晶質合金理論………………………………...18
2.6.1 等莫耳多元合金簡介………………………...18
2.6.2 多元合金自由能……………………………...19
2.7 有關等莫耳多元合金之研究…………………………...20
2.7.1 等莫耳比多元合金系統之研究……………...20
2.7.2 高亂度合金微結構及性質探討……………...22
2.8 本篇論文研究目的……………………………………...24
三、 實驗方法………………………………………………………26
3.1 等莫耳多元合金組成…………………………………...26
3.2 合金製備………………………………………………...29
3.3 微結構觀察……………………………………………...29
3.4 X光繞射分析……………………………………………32
3.5 機械性質量測…………………………………………...32
3.6 實驗流程圖……………………………………………...32
四、 結果與討論……………………………………………………34
4.1 微結構分析……………………………………………...34
4.1.1 FCC等莫耳多元合金系統…………………...34
4.1.2 含3 at % B FCC等莫耳多元合金系統………49
4.1.3 BCC等莫耳多元合金系統…………………...58
4.1.4 含3 at % B BCC等莫耳多元合金系統………79
4.1.5 FCC及BCC混合等莫耳十四元合金系統…...89
4.1.6 分相現象及元素間互溶之族群……………...97
4.1.7 X光繞射分析及非晶質相的存在…………..100
4.2 機械性質分析………………………………………….115
4.2.1 FCC等莫耳多元合金系統硬度值………….115
4.2.2 BCC等莫耳多元合金系統硬度值………….118
五、 結論…………………………………………………………..123
六、 參考文獻……………………………………………………..126

1. 黃國雄, "等莫耳比多元合金系統之研究", 國立清華大學材料科學工程研究所碩士論文, 1996.
2. 賴高廷, "高亂度合金微結構及性質探討", 國立清華大學材料科學工程研究所碩士論文, 1998.
3. J. Kramer, Z. Phys., Vol 106, 1937, pp 639.
4. J. Kramer, Annln Phys., Vol 37, 1934, pp 19.
5. A. Bremer, D. E. Couch and E. K. Williams, J. Res. Natn. Bur. Stand., Vol 44, 1950, pp 109.
6. P. Duwes, Trans. Am. Soc. Metals, Vol 60, 1967, pp 607.
7. H. W. Kui, A. L. Greer and D. Turnbull, "Formation of Bulk Metallic-Glass by Fluxing", Applied Physics Letters, Vol 45, Iss 6, 1984, pp 615-616.
8. A. Inoue, K. Kita, T. Masumoto and K. Ohtera, "New Amorphous-Alloys with Good Ductility in Al-Ce-NB, Al-Ce-Fe, Al-Ce-Co, Al-Ce-Ni, Al-Ce-Cu Systems", Japanese Journal of Applied Physics Part 2-Letters, Vol 27, Iss 10, 1998, pp 1796-1799.
9. A. Inoue, K. Kita, T. Masumoto and T. Zhang, "An Amorphous La-55-Al-25-Ni-20 Alloy Prepared by Water Quenching", Materials Transactions JIM, Vol 30, Iss 9, 1989, pp 722-725.
10. A. Inoue-A, T. Zhang and T. Masumoto, "Zr-Al-Ni Amorphous-Alloys with High Glass-Transition Temperature and Significant Supercooled Liquid Region", Materials Transactions JIM, Vol 31, Iss 3, 1990, pp 177-183.
11. A. Inoue and T. Masumoto, U.S. Patent No. 5032196, Japanese Patent 07-122120.
12. A. Peker and W. L. Johnson, "A Highly Processable Metallic-Glass - Zr41.2Ti13.8Cu12.5Ni10.0Be22.5", Applied Physics Letters, Vol 63, Iss 17, 1993, pp 2342-2344.
13. A. Inoue, T. Zhang, K. Ohba and T. Shibata, "Continuous-Cooling-Transformation (CCT) Curves for Zr-Al-Ni-Cu Supercooled Liquids to Amorphous or Crystalline Phase", Materials Transactions JIM, Vol 36, Iss 7, 1995, pp 876-878.
14. A. Inoue and J. S. Gook, "Multicomponent Fe-Based Glassy Alloys with Wide Supercooled Liquid Region Before Crystallization", Materials Transactions JIM, Vol 36, Iss 10, 1995, pp 1282-1285.
15. A. Inoue, N. Nishiyama and T. Matsuda, "Preparation of Bulk Glassy Pd40Ni10Cu30P20 Alloy of 40 mm in Diameter by Water Quenching", Materials Transactions JIM, Vol 37, Iss 2, 1996, pp 181-184.
16. Y. He, T. D. Shen, R. B. Schwarz, "Bulk Amorphous Metallic Alloys - Synthesis by Fluxing Techniques and Properties", Metallurgical and Materials Transactions A-Physical Metallurgy and Materials Science, Vol 29, Iss 7, 1998, pp 1795-1804.
17. T. Zhang and A. Inoue, "Thermal and Mechanical-Properties of Ti-Ni-Cu-Sn Amorphous-Alloys with a Wide Supercooled Liquid Region Before Crystallization", Materials Transactions JIM, Vol 39, Iss 10, 1998, pp 1001-1006.
18. A. Inoue and T. Zhang, Materials Transactions JIM, Vol 40, 1999, pp 301.
19. A. Inoue, T. Zhang and A. Takeuchi, "Bulk Amorphous-Alloys with High Mechanical Strength and Good Soft-Magnetic Properties in Fe-TM-B (Tm=iv-VIII Group Transition-Metal) System", Applied Physics Letters, Vol 71, Iss 4, 1997, pp 464-466.
20. A. Inoue, T. Nakamura, N. Nishiyama and T. Masumoto, "Mg-Cu-Y Bulk Amorphous-Alloys with High-Tensile Strength Produced by a High-Pressure Die-Casting Method", Materials Transactions JIM, Vol 33, Iss 10, 1992, pp 937-945.
21. A. Inoue, T. Nakamura, T. Sugita, T. Zhang and T. Masumoto, "Bulky La-Al-TM (TM = Transition-Metal) Amorphous-Alloys with High-Tensile Strength Produced by a High-Pressure Die-Casting Method", Materials Transactions JIM, Vol 34, Iss 4, 1993, pp 351-358.
22. A. Inoue and T. Zhang, "Fabrication of Bulk Glassy Zr55Al10Ni5Cu30 Alloy of 30 mm in Diameter by a Suction Casting Method", Materials Transactions JIM, Vol 37, Iss 2, 1996, pp 185-187.
23. A. Inoue, N. Nishiyama and H. Kimura, "Preparation and Thermal-Stability of Bulk Amorphous Pd40Cu30Ni10P20 Alloy Cylinder of 72 mm in Diameter", Materials Transactions JIM, Vol 38, Iss 2, 1997, pp 179-183.
24. A. Inoue, Bulk Amorphous Alloys, Vol 2, Trans Tech Publications, Zurich, 1999, pp 28.
25. A. Inoue and N. Nishiyama, "Extremely Low Critical Cooling Rates of New Pd-Cu-P Base Amorphous-Alloys", Materials Science and Engineering A-Structural Materials Properties Microstructure and Processing, Vol 226, Iss JUN, 1997, pp 401-405.
26. H. S. Chen, H. J. Leamy and C. E. Miller, "Preparation of Glassy Metals", Annual Review of Materials Science, Vol 10, 1980, pp 363-391.
27. B. B. Prasad, T. R. Anantharaman, A. K. Bhatnagar, D. Ganesan and R. Jagannathan, "A Mossbauer Study of Amorphous Alloy Fe67Co18B14Si1", Journal of Non-crystalline Solids, Vol 61-2, Iss JAN, 1984, pp 391-395.
28. Carlisle and H. Ben, "Neodymium Challenges Ferrite Magnets", Machine Design, Vol 58, No 1, 1986, pp 24-30.
29. H. Jones, Rapid Solidification of Metals and Alloys, Inst. Of Metallurgists, London, 1982.
30. F. G. Yost, "On the Use of Ti50Be40Zr10 As a Spring Material", Journal of Materials Science, Vol 16, Iss 11, 1981, pp 3039-3044.
31. P. Haasen, "Metallic Glasses", Journal of Non-Crystalline Solids, Vol 56, Iss 1-3, 1983, pp 191-199.
32. D. E. Polk and B. C. Giessen, in Rapid Solidification Technology Source Book, ASM, Metals Park, Ohio, 1983.
33. F. E. Luborsky, "Amorphous Metallic Alloys", Butterworths Monographs in Materials, London, UK, 1983, pp 19-20.
34. D. A. Porter and K. E. Easterling, "Phase Transformations in Metals and Alloys", Chapman and Hill, New York, USA, 1991, pp 186-197.
35. D. A. Porter and K. E. Easterling, "Phase Transformations in Metals and Alloys", Chapman and Hill, New York, USA, 1991, pp 287-291.
36. D. R. Uhlmann, "A Kinetic Treatment of Glass Formation", Journal of Non-Crystalline Solids, Vol 7, 1972, pp 337-348.
37. A. Inoue, T. Zhang and T. Masumoto, "Glass-Forming Ability of Alloys", Journal of Non-Crystalline Solids, Vol 156, Iss MAY, 1993, pp 473-480.
38. A. Inoue and T. Zhang, Material Transaction JIM, Vol 40, 1999, pp 301.
39. H. Wang, R. Luck and B. Predel, "Thermodynamic Calculations in Quaternary Transition-Metal Systems", Journal of Alloys and Compounds, Vol 191, Iss 1, 1993, pp 43-49.
40. R. Luck, Z. C. Wang and B. Predel, "A Survey of New and Known Models for the Estimation of Mixing Enthalpies of Multicomponent Systems", Journal of Non-Crystalline Solids, Vol 117, Iss FEB, 1990, pp 529-532.
41. L. Battezzati, "Thermodynamics of Undercooled Melts and Metastable Phase-Formation", Materials Science and Engineering A-Structural Materials Properties Microstructure and Processing, Vol 178, Iss 1-2, 1994, pp 43-49.
42. R. Luck, U. Gerling and B. Predel, "On the Interpolation Algorithms for Thermodynamic Functions of Mixtures in Multicomponent Systems from Binary Boundary Systems", Zeitschrift fur Metallkunde, Vol 77, Iss 7, 1986, pp 442-448.
43. M. Hillert, "Empirical-Methods of Predicting and Representing Thermodynamic Properties of Ternary Solution Phases", Calphad-Computer Coupling of Phase Diagrams and Thermochemistry, Vol 4, Iss 1, 1980, pp 1-12.
44. R. Q. Li, "The Application of R Function to New Asymmetric Model and Toop Model", Calphad-Computer Coupling of Phase Diagrams and Thermochemistry, Vol 13, Iss 1, 1989, pp 67-70.
45. L. Kaufman and H. Berstein, Computer Calculation of Phase Diagrams, Academic Press, New York, 1970.