臺灣博碩士論文加值系統

本研究探討退火對Fe76Si10B10Cr2Y2非晶薄帶軟磁性質之影響。以單輥熔射旋淬法製備成份Fe76Si10B10Cr2Y2之五元合金薄帶，並以快速升溫退火系統(RTP)，在真空下進行持溫退火，並設定不同溫度、時間等參數進行退火，分析其微觀結構及軟磁性質之變化。利用X光繞射儀(XRD)及掃描式電子顯微鏡(SEM)進行微觀結構分析。以同步熱分析儀(Simultaneous TGA/DSC)分析材料之特徵溫度，並藉由Kissinger方程式算出結晶活化能大小。以振動樣品磁力儀(VSM)量測薄帶之飽和磁化強度(Ms)及矯頑磁力(Hc)。以熱磁分析儀(TMA)量測薄帶之居禮溫度(Tc)。
實驗結果顯示，鑄態薄帶之飽和磁化強度為1.25 T，矯頑磁力為22.84 A/m，居禮溫度為564.4 K。鑄態薄帶經過適當溫度與時間退火後，其飽和磁化強度上升且矯頑磁力下降，顯示退火處理有助於軟磁性質的提升，最佳退火溫度與時間為500°C退火3分鐘，飽和磁化強度為1.37 T，矯頑磁力為1.11 A/m。

In this investigation, we explored the influence of annealing treatment on soft magnetic properties of Fe76Si10B10Cr2Y2 amorphous ribbon. Alloy ribbon with composition of Fe76Si10B10Cr2Y2 was synthesized by the single roller melt-spinning method. Microstructures were examined by XRD and SEM. To examine the thermal properties, the as-cast ribbon was measured with Simultaneous TGA/DSC. Kissinger plot method was used to obtain the activation energy of crystallization. Soft magnetic properties and Curie temperature were measured by VSM and TMA, respectively.
The magnetic measurements of the as-cast ribbon contained Ms, Hc and Tc. The value of Ms was 1.25 T, Hc was 22.84 A/m and Tc was 564.4 K. The soft magnetic properties of the optimum parameter for the annealing temperature and annealing time was at 500°C for 3 minutes, Ms was 1.37 T and Hc was 1.11 A/m. Therefore, the annealing treatment could improve the soft magnetic properties of the alloy ribbon.

摘 要 i
ABSTRACT ii
誌 謝 iii
目 錄 iv
表目錄 vii
圖目錄 viii
第一章 前言 1
1.1 非晶質合金 1
1.2 研究動機與目的 3
第二章 文獻回顧與理論基礎 5
2.1 非晶質合金之發展歷史 5
2.2 非晶質合金之製備方式 9
2.3 非晶質合金之種類 11
2.4 鐵基非晶質合金 13
2.5 非晶質合金之成份組成條件 14
2.5.1 實驗歸納法則 15
2.5.2 熱力學觀點 16
2.6 非晶質合金之熱力學特性 17
2.6.1 玻璃轉換溫度 17
2.6.2 居禮溫度 20
2.7 評估玻璃形成能力之參數 21
2.7.1 過冷液態區間ΔTx=Tx-Tg 21
2.7.2 簡約玻璃轉變溫度Trg =Tg/Tl 22
2.7.3 γ參數γ=Tx/ (Tg+Tl ) 24
2.8 熱分析動力學 26
2.9 磁性理論 26
2.9.1 磁性之分類 27
2.9.2 磁異向性 34
2.9.3 非晶軟磁特性 35
第三章 實驗流程與方法 38
3.1 實驗流程 38
3.2 合金薄帶之製備 39
3.2.1 合金成份配製 39
3.2.2 母合金熔煉 39
3.2.3 合金薄帶製作 40
3.2.4 合金薄帶熱處理 41
3.3 材料分析 43
3.3.1 X光繞射儀 43
3.3.2 同步熱分析儀 44
3.3.3 掃描式電子顯微鏡與能量分散質譜儀 45
3.3.4 振動樣品磁力儀 46
3.3.5 居禮溫度量測 48
第四章 結果與討論 49
4.1 試片外觀之觀察 49
4.1.1 母合金鑄錠之外觀 49
4.1.2 合金薄帶之外觀 49
4.2 Fe76Si10B10Cr2Y2合金之結構分析 50
4.2.1 母合金鑄錠之XRD分析 50
4.2.2 合金薄帶之XRD分析 51
4.2.3 合金薄帶之SEM觀察 52
4.3 Fe76Si10B10Cr2Y2合金薄帶之熱性質分析 53
4.3.1 一般之非恆溫分析法-Kissinger plot 55
4.4 Fe76Si10B10Cr2Y2合金薄帶之磁性質分析 57
4.4.1 磁滯曲線 57
4.4.2 居禮溫度 59
4.5 熱處理後Fe76Si10B10Cr2Y2合金薄帶之分析 60
4.5.1 退火後合金薄帶之XRD分析 60
4.5.2 退火後合金薄帶之SEM觀察 64
4.5.3 退火後合金薄帶之軟磁性質分析 65
4.6 退火對Fe76Si10B10Cr2Y2合金薄帶結構的影響 77
4.7 退火對Fe76Si10B10Cr2Y2合金薄帶軟磁性質的影響 77
第五章 結論 78
第六章 未來工作與建議 79
參考文獻 80

[1]吳學陞，「新興材料-塊狀非晶質金屬材料」，工業材料，第149期，第154頁，1999。
[2]A. Inoue, T. Zhang, and T. Masumoto, "Preparation of Bulky Amorphous Zr-Al- Co-Ni-Cu Alloys by Copper Mold Casting and Their Thermal and Mechanical Properties," Materials Transactions, JIM, vol. 36, pp. 391-398, 1995.
[3]A. Inoue, "High Strength Bulk Amorphous Alloys with Low Critical Cooling Rates," Materials Transactions, JIM, vol. 36, pp. 866-875, 1995.
[4]A. Inoue, "Bulk Amorphous Alloys-Practical Characteristics and Applications," Materials Science Foundations, vol. 6, pp. 1, 1999.
[5]A. Inoue and T. Zhang, "Impact Fracture Energy of Bulk Amorphous Zr55Al10Cu30Ni5 Alloy," Materials Transactions, JIM, vol. 37, pp. 1726-1730, 1996.
[6]A. Inoue, N. Nishiyama, and T. Matsuda, "Preparation of Bulk Glassy Pd40Ni10Cu30P20 Alloy of 40mm in Diameter by Water Quenching," Materials Transactions, JIM, vol. 37, pp. 185-187, 1996.
[7]S. Pang, T. Zang, H. Kimura, K. Asami, and A. Inoue, "Corrosion Behavior of Zr-(Nb-)Al-Ni-Cu Glassy Alloys," Materials Transactions, JIM, vol. 41, pp. 1490-1494, 2000.
[8]H. Habazaki, H. Ukai, K. Izumiya, and K. Hashimoto, "Highly corrosion-resistant Ni-based bulk amorphous alloys," Materials Science & Engineering A, vol. 304-306, pp. 753-757, 2001.

[9]T. C. Chieh, J. Chu, C. T. Liu, and J. K. Wu, "Corrosion of Zr52.5Cu17.9Ni14.6Al10Ti5 bulk metallic glasses in aqueous solutions," Materials Letters, vol. 57, pp. 3022-3025, 2003.
[10]B.-M. Im, E. Akiyama, H. Habazaki, A. Kawashima, K. Asami, and K. Hashimoto, "The effect of phosphorus addition on the corrosion behavior of amorphous Fe-8Cr-P alloys in 9M H2SO4," Corrosion Science, vol. 37, pp. 709-722, 1995.
[11]H. Habazaki, H. Ukai, K. Izumiya, and K. Hashimoto, "Corrosion behaviour of amorphous Ni–Cr–Nb–P–B bulk alloys in 6M HCl solution," Materials Science & Engineering A, vol. 318, pp. 77-86, 2001.
[12]A. Gebert, U. Wolff, A. John, and J. Eckert, "Corrosion behavior of Mg65Y10Cu25 metallic glass," Scripta Materialia, vol. 43, pp. 279-283, 2000.
[13]W. H. Peter, R. A. Buchanan, C. T. Liu, P. K. Liaw, M. L. Morrison, J. A. Horton, C.A. Carmichael Jr. and J.L. Wright, "Localized corrosion behavior of a zirconium-based bulk metallic glass relative to its crystalline state," Intermetallics, vol. 10, pp. 1157-1162, 2002.
[14]A. Inoue, H. Koshiba, T. Zhang, and A. Makino, "Wide supercooled liquid region and soft magnetic properties of Fe56Co7Ni7Zr0-10Nb(or Ta)0-10B20amorphous alloys," Journal of applied physics, vol. 83, pp. 1967-1974, 1998.
[15]Y. Hara, T. Ando, R. C. O''Handley, and N. J. Grant, "Fine-particle magnetism in the devitrified metallic glass Fe43Cr25Ni20B12," Journal of applied physics, vol. 62, pp. 1948-1951, 1987.
[16]A. Inoue, "Bulk amorphous alloys with soft and hard magnetic properties," Materials Science & Engineering A, vol. 226-228, pp. 357-363, 1997.
[17]A. Inoue and J. S. Gook, "Fe-Based Ferromagnetic Glassy Alloys with Wide Supercooled Liquid Region," Materials Transactions, JIM, vol. 36, pp. 1180-1183, 1995.
[18]A. Inoue and J. S. Gook, "Effect of Additional Elements(M) on the Thermal Stability of Supercooled Liquid in Fe72-xAl5Ga2P11C6B4Mx Glassy Alloys," Materials Transactions, JIM, vol. 37, pp. 32-38, 1996.
[19]A. Inoue, M. Koshiba, T. Itoi, and A. Makino, "Ferromagnetic Co-Fe-Zr-B amorphous alloys with glass transition and good high-frequency permeability," Applied Physics Letters, vol. 73, pp. 744-746, 1998.
[20]A. Inoue and B. L. Shen, "Formation and Soft Magnetic Properties of Co-Fe-Si- B-Nb Bulk Glassy Alloys," Materials Transactions, JIM, vol. 43, pp. 1230-1234, 2002.
[21]A. Inoue and B. L. Shen, "Soft Magnetic Bulk Glassy Fe-B-Si-Nb Alloys with High Saturation Magnetization above 1.5T," Materials Transactions, JIM, vol. 43, pp. 766-769, 2002.
[22]B. L. Shen, C. Chang, and A. Inoue, "Formation, ductile deformation behavior and soft-magnetic properties of (Fe,Co,Ni)-B-Si-Nb bulk glassy alloys," Intermetallics, vol. 15, pp. 9-16, 2007.
[23]H. X. Li, H. Y. Jung, and S. Yi, "Glass forming ability and magnetic properties of bulk metallic glasses Fe68.7-xC7.0Si3.3B5.5P8.7Cr2.3Mo2.5Al2.0Cox (x=0-10)," Journal of Magnetism and Magnetic Materials, vol. 320, pp. 241-245, 2008.
[24]A. Inoue, "Bulk amorphous and nanocrystalline alloys with high functional properties," Mater. Sci. Eng., A, vol. 304, pp. 1-10, 2001.

[25]M. Hagiwara, A. Inoue, and T. Masumoto, "Mechanical properties of Fe-Si-B amorphous wires produced by in-rotating-water spinning method," Metallurgical and Materials Transactions A, vol. 13, pp. 373-382, 1982.
[26]A. Inoue, T. Zhang, and A. Takeuchi, "Ferrous and Nonferrous Bulk Amorphous Alloys," Materials Science Forum, vol. 269-272, pp. 855-864, 1998.
[27]J. M. Park, J. S. Park, J. H. Na, D. H. Kim, and D. H. Kim, "Effect of Y addition on thermal stability and the glass forming ability in Fe-Nb-B-Si bulk glassy alloy," Materials Science and Engineering A, vol. 435-436, pp. 425-428, 2006.
[28]Z. L. Long, Y. Shao, X. H. Deng, Z. C. Zhang, Y. Jiang, P. Zhang, et al., "Cr effects on magnetic and corrosion properties of Fe-Co-Si-B-Nb-Cr bulk glassy alloys with high glass-forming ability," Intermetallics, vol. 15, pp. 1453-1458, 2007.
[29]Z. Long, Y. Shao, F. Xu, H. Wei, Z. Zhang, P. Zhang, et al., "Y effects on magnetic and mechanical properties of Fe-based Fe–Nb–Hf–Y–B bulk glassy alloys with high glass-forming ability," Materials Science and Engineering B, vol. 164, pp. 1-5, 2009.
[30]A. Takeuchi and A. Inoue, "Classification of bulk metallic glasses by atomic size difference, heat of mixing and period of constituent elements and its application to characterization of the main alloying element," Mater. Trans., vol. 46, pp. 2817-2829, 2005.
[31]王一禾、楊膺善，非晶態合金，北京：冶金工業出版社，第346頁，1988。
[32]W. Klement, R. H. Wilens, and P. Duwez, "Non-crystalline Structure in Solidified Gold-Silicon Alloys," Nature, vol. 187, pp. 869-870, 1960.
[33]P. Duwez and R. H. Willens, "Rapid quenching of liquid alloys," Trans. Met. Soc., vol. 227, pp. 362-365, 1963.
[34]H. S. Chen and D. Turnbull, "Evidence of a Glass-Liquid Transition in a Gold- Germanium-Silicon Alloy," Journal of Chemical Physics, vol. 48, pp. 2560-2566, 1968.
[35]H. S. Chen and C. E. Miller, "A Rapid Quenching Technique for the Preparation of Thin Uniform Films of Amorphous Solids," Review of Scientific Instruments, vol. 41, pp. 1237-1242, 1970.
[36]H. Liebermann and J. C. Graham, "Production of amorphous alloy ribbons and effects of apparatus parameters on ribbon dimensions," IEEE Trans. Mag., vol. 12, pp. 921-923, 1976.
[37]Mustafa Kamal and Usama S. Mohammad, A Review:Chill-Block Melt Spin Technique,Theoris & Applications, Bentham Science Publishers, pp 9, 2012.
[38]A. Inoue, "Stabilization of metallic supercooled liquid and bulk amorphous alloys," Acta Materialia, vol. 48, pp. 279-306, 2000.
[39]A. Inoue and A. Takeuchi, "Recent development and applications of bulk glassy alloys," IJAGS, vol. 1(3), pp. 273-295, 2010.
[40]A. Inoue and R. E. Park, "Soft Magnetic Properties and Wide Supercooled Liquid Region of Fe-P-B-Si Base Amorphous Alloys," Mater. Trans., vol. 37, pp. 1715-1721, 1996.
[41]P. Duwez and S. C. H. Lin, "Amorphous Ferromagnetic Phase in Iron-Carbon- Phosphorus Alloys," Journal of applied physics, vol. 38, pp. 4096-4097, 1967.
[42]Y. Yoshizawa, S. Oguma, and K. Yamauchi, "New Fe‐based soft magnetic alloys composed of ultrafine grain structure," J. Appl. Phys, vol. 64, pp. 6044-6046, 1988.
[43]A. Inoue, "A.High-strength bulk amorphous-alloys with low critical cooling rates," Mater. Trans. JIM, vol. 36, pp. 866-875, 1995.
[44]D. S. Song, J.-H. Kim, E. Fleury, W. T. Kim, and D. H. Kim, "Synthesis of ferromagnetic Fe-based bulk glassy alloys in the Fe–Nb–B–Y system," Journal of Alloys and Compounds, vol. 389, pp. 159-164, 2005.
[45]T. Zhang, F. Liu, S. Pang, and R. Li, "Ductile Fe-Based Bulk Metallic Glass with Good Soft-Magnetic Properties," Materials Transactions, JIM, vol. 48 (5), pp. 1157-1160, 2007.
[46]B. Shen, M. Akiba, and A. Inoue, "Effects of Si and Mo additions on glass-forming in FeGaPCB bulk glassy alloys with high saturation magnetization," PHYSICAL REVIEW B, vol. 73, pp. 104204, 2006.
[47]A. Inoue, B. L. Shen, A. R. Yavari, and A. L. Greer, "Mechanical properties of Fe-based bulk glassy alloys in Fe–B–Si–Nb and Fe–Ga–P–C–B–Si systems," Journal of Materials Research, vol. 18, pp. 1487-1492, 2003.
[48]C. Chang, T. Kubota, A. Makinoa, and A. Inoue, "Synthesis of ferromagnetic Fe-based bulk glassy alloys in the Fe–Si–B–P–C system," Journal of Alloys and Compounds, vol. 473, pp. 368-372, 2009.
[49]A. Inoue and B. Shen, "New Fe-based bulk glassy alloys with high saturated magnetic flux density of 1.4–1.5 T," Materials Science and Engineering A, vol. 375–377, pp. 302-306, 2004.
[50]S. L. Lin, S. F. Chen, J. K. Chen, and Y. L. Lin, "Formation and magnetic properties of Fe-Si-B-Dy amorphous alloy," Intermetallics, vol. 18, pp. 1826-1828, 2010.


[51]C. Chang, C. Qin, A. Makino, and A. Inoue, "Enhancement of glass-forming ability of FeSiBP bulk glassy alloys with good soft-magnetic properties and high corrosion resistance," Journal of Alloys and Compounds, vol. 533, pp. 67-70, 2012.
[52]A. Inoue and K. Hashimoto, Amorphous and Nanocrystalline Material: Preparation, Properties, and Applications. New York: Springer, pp. 4-5, 2000.
[53]Z. P. Lu and C. T. Liu, "A new approach to understanding and measuring glass formation in bulk amorphous materials," Intermetallics, vol. 12, pp. 1035-1043, 2004.
[54]L. Liu, X. Zhao, C. Ma, and T. Zhang, "Kinetics of crystallization process for Pd-based bulk metallic glasses," Intermetallics, vol. 17, pp. 241-245, 2009.
[55]W. D. Callister, Materials science and engineering an introduction, 7th ed. Wiley India Pvt Ltd, pp. 546, 2007.
[56]A. Inoue, T. Zhang, and T. Masumoto, "Glass-forming ability of alloys," J Non-cryst Solids, vol. 156-158, pp. 473-480, 1993.
[57]D. Turbull and J. C. Fisher, "Rate of Nucleation in Condensed Systems," J. Chem. Phys., vol. 17, pp. 71-73, 1949.
[58]Z. P. Lu, H. Tan, Y. Li, and S. C. Ng, "The correlation between reduced glass transition temperature and glass forming ability of bulk metallic glasses," Scripta Mater., vol. 42, pp. 667-673, 2000.
[59]Z. P. Lu and C. T. Liu, "A new glass-forming ability criterion for bulk metallic glasses," Acta Mater., vol. 50, pp. 3501-3512, 2002.


[60]P. Altlizar and R. Valenzuela, "Avrami and Kissinger theories for crystallization of metallic amorphous alloys," Mater. Lett., vol. 11, pp. 101-104, 1991.
[61]D. R. Askel, P. P. Phule, The Science and Enginering of Materials, 5th, edition, CENGAGE, Learning, pp. 768, 2006.
[62]陳俊明，微量Pd對Fe-Si-B非晶合金之玻璃形成能力及軟磁性質研究，碩士論文，國立臺北科技大學材料科學與工程研究所，台北，2012。
[63]D. C. Jiles, "Recent advances and future directions in magnetic materials," Acta Mater., vol. 51, pp. 5907-5939, 2003.
[64]張煦、李學養譯，磁性物理學，台北：聯經出版事業公司，第143頁，1981。
[65]B. D. Cullity and C. D. Graham, Introduction to Magnetic Materials, 2th ed. Wiley- IEEE Press, pp. 197-238, 2008.
[66]G. Herzer, "Nanocrystalline soft magnetic alloys," Handbook of Magnetic Material, vol. 10(3), pp. 435-439, 1997.
[67]高汝偉、馮維存、王標、陳偉、韓廣兵、張鵬、劉漢強、李衛、郭永權、李岫梅，「奈米複合永磁材料的有效各向異性與矯頑力」，物理學報，第52期，第703-706頁，2003。
[68]周壽增、董清飛，超強永磁體-稀土鐵性永磁材料，第二版，中國:冶金工業出版社，第39頁，2004。
[69]吳柏勳，Fe-Mn-Si-B-Cu合金的玻璃形成能力與軟磁性質研究，碩士論文，國立臺北科技大學材料科學與工程研究所，台北，2012。
[70]張正武，FePt及FePtB奈米晶薄帶磁性、相變化與交換耦合效應之研究，碩士論文，國立中正大學物理研究所，嘉義，2003。
[71]D. B. Miracle, "A structural model for metallic glasses," Nature Mater., vol. 3, pp. 697-702, 2004.
[72]A. Zaluska and H. Matyja, "Crystallization characteristics of amorphous Fe-Si-B alloys," JOURNAL OF MATERIALS SCIENCE, vol. 18, pp. 2163-2172, 1983.
[73]R. Sahingoz, M. Erol, and M. R. J. Gibbs, "Observation of changing of magnetic properties and microstructure of metallic glass Fe78Si9B13 with annealing," Journal of Magnetism and Magnetic Materials, vol. 271, pp. 74-78, 2004.