臺灣博碩士論文加值系統

鋯基非晶質合金在科學研究及運用上具有重要的特性，諸如高玻璃形成能力（glass-forming ability）及在低的臨界冷卻速率下仍有寬廣的過冷區域（super-cooled liquid region），且在工程運用上具有良好機械性質如高的拉伸強度（tensile strength）、彈性模數（elastic modulus）、衝擊破壞能（impact fracture energy）及抗腐蝕能力（corrosion resistance）等優異的工程特性。日本東北大學Inoue 與Masumoto 等二位教授曾提出「增加原子的堆積密度可有效的提昇非晶質合金的熱穩定性及機械強度」。故本研究即選用ZrNiAlCu非晶質合金添加較小的原子"硼"增加其堆積密度，且在低冷卻速率下製作試片，研究其熱穩定性及玻璃形成能力。
本實驗選用Zr、Al、Cu、Ni等純元素為主要成分，添加不同原子百分比的硼元素，調製所需的合金Zr65-xAl7.5Cu17.5Ni10Bx（X＝0，2，4，6，8，10），在氬氣氛爐內利用電弧熔解（arc melting）及墜落鑄造（drop cast）方式於水冷銅模中，製成厚度0.5~2 mm的試片並利用單輥輪旋轉熔鑄（single roller melt spinning）技術製作厚約100~200μm的薄帶。在儀器分析方面使用X光繞射儀（X－ray diffraction，XRD）、掃描式電子顯微鏡（scanning electron microscopy，SEM ）、穿透式電子顯微鏡（transmission electron microscopy，TEM）、熱差分析（differential thermal analysis，DTA）、示差掃描熱量計（differential scanning calorimetry，DSC）、高溫顯微鏡（hot stage optical microscopy）等研究合金的玻璃形成能力及熱穩定性並觀察其結晶行為與顯微結構的變化。
由實驗結果得知，Zr65-xAl7.5Cu17.5Ni10Bx可在較低的冷卻速率下獲得非晶質相。在顯微組織分析上，發現於部分非晶質基地內夾雜著奈米晶粒，其尺寸約為10 nm，並經鑑定此奈米晶結構為四面體的CuZr2型結晶（Tetragonal CuZr2 type）。在熱性質分析方面，其簡化玻璃溫度（Trg）高達0.55；玻璃轉換溫度（Tg）與結晶溫度（Tx）隨著硼元素的增加有上昇的趨勢，△Tx於添加4 at.%及6 at.%時出現最大值約為86℃，較基材為高；活化能（Kissinger plot）以添加2 at.﹪的硼元素時（X＝2）最高，約為360 ±10 KJ/mol，較基材高約20﹪，顯見添加硼元素有助於提昇鋯基非晶質合金的玻璃形成能力及熱穩定性；在結晶動力分析部分，Avrami exponent值介於1.5~2.5之間，且由C.Wagner 提出之理論獲得証明，其結晶成長行為屬受擴散控制之成長機制，成核速率成遞減模式。

The Zr-base amorphous alloy has many significant features in scientific research and application, such as high glass-forming ability and wide super-cooled liquid region under low critical cooling rate. In engineering application, it provides good mechanical properties, such as high tensile strength, high elastic modulus, relatively high impact fracture energy and excellent corrosion resistance. Inoue and Masunoto （Northeast University, Japan） declared that “To increase atomic packing density can improve the thermal stability and mechanic strength in amorphous alloy”. Therefore, this research is focused on studying the thermal stability and glass-forming ability by increasing packing density of ZrNiAlCu amorphous alloy with adding smaller atom Boron. The test film was prepared under low cooling rate.
In the experiment, Zr, Al, Cu and Ni pure element were selected as the main components and different atom percent of Boron was added to produce Zr65-xAl7.5Cu17.5Ni10Bx（X＝0，2，4，6，8，10）. Specimens with 0.5-2 mm thickness were prepared by arc melting under the Argon atmosphere furnace and drop cast in a water-cooled copper mold. Then ribbons of 100~200μm thickness were prepared by single roller melt spinning technology. Different techniques, such as X-Ray Diffraction （XRD）, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Differential Thermal Analysis (DTA), Differential Scanning Calorimetry (DSC) and Hot Stage Optical Microscopy were utilized to study the glass-forming ability and thermal stability of these alloys and to observe their changes in crystallization behavior and microstructure.
From the experimental results, it is shown that Zr65-xAl7.5Cu17.5Ni10Bx can obtain amorphous phase under lower cooling rate. By the microstructure analysis, some nanocrystalline phases with size approximate 10 nm are found in some areas of the amorphous matrix. The nanocrystalline phase is recognized to the tetragonal CuZr2 type crystal. According to the thermal stability analysis, we found Reduced Glass Temperature （Trg）is up to 0.55 in this study. Glass Transition Temperature （Tg） and Crystalline Temperature （Tx） raise with the Boron addition. Not only 4 at. % but also 6 at. % Boron addition, △Tx of this crystal have maximum values, approximately 86℃. They are higher than that of base alloy. Activation energy（Kissinger plot）with the 2 at.﹪of Boron addition （X＝2） reaches the highest value, 360 ± 10 KJ/mol, which is 20% higher than that of base alloy. Obviously, inserting Boron element can improve the glass-forming ability and thermal stability of the Zr-base amorphous alloy. From the crystallization kinetics analysis, we acquired the result of Avrami exponent is between 1.5-2.5. We also verify that the mechanism of crystallization growth behavior is diffusion control model of C.Wagner’s theory with a decreasing nucleation rate.

總目錄
頁次
中文摘要…………………………………………………………………………Ⅰ
英文摘要…………………………………………………………………………Ⅲ
致謝………………………………………………………………………………Ⅴ
總目錄……………………………………………………………………………Ⅵ
圖目錄……………………………………………………………………………Ⅹ
表目錄…………………………………………………………………………ⅩⅣ
第一章 前言……………………………………………………………………....1
第二章 理論基礎………………………………………………………………....4
2.1 概述……………………………………………………………………….4
2.2 塊狀非晶質合金發展歷程……………………………………………….5
2.3 非晶質合金的種類與特性……………………………………………….6
2.3.1 非晶態合金的種類………………………………………………….6
2.3.2 非晶質合金的特性………………………………………………….8
2.3.2.1 機械性質……………………………………………………...11
2.3.2.2 化學性質--耐蝕性…………………………………………...16
2.3.2.3 軟磁性………………………………………………………...18
2.3.2.4 其他重要性質………………………………………………...19
2.4 非晶質合金的製造方法………………………………………………...19
2.5 非晶質的形成條件……………………………………………………...20
2.6 非晶質的熱力學特性…………………………………………………...23
2.6.1 非晶質是平衡的介穩……………………………………………...23
2.6.2 玻璃轉換溫度（Tg）……………………………………………….24
2.6.3 簡化玻璃溫度（Trg） ……………………………………………..27
2.7 非晶質形成的熱力學及結構因素 …………………………………….27
2.7.1 合金效應 …………………………………………………………28
2.7.2 原子相互作用 ……………………………………………………28
2.7.3 尺度效應 …………………………………………………………33
2.7.4 化學鍵能 …………………………………………………………34
2.8 非晶質合金的熱穩定性 ……………………………………………….34
2.8.1 非晶質合金的壽命 ………………………………………………35
2.8.2 化學反應與結晶活化能 …………………………………………37
2.9 結晶動力學 …………………………………………………………….38
2.9.1 恆溫結晶 ………………………………………………………….38
2.9.2 晶粒成長控制機制………………………………………………...40
第三章 實驗流程….……………………………………………………………43
3.1 合金組成 ……………………………………………………………….43
3.2 合金熔煉與試片製作 ………………………………………………….44
3.2.1 墜落鑄造 …………………………………………………………44
3.2.2 薄帶製作 …………………………………………………………45
3.2.3 試片取樣 …………………………………………………………45
3.3 顯微組織分析 …………………………………………………………46
3.3.1 光學顯微鏡（OM） …………………………………………………46
3.3.2 掃描式電子顯微鏡（SEM）與EDS …………………………….….46
3.3.3 穿透式電子顯微鏡（TEM） ………………………………………..47
3.3.4 X-光繞射儀（XRD）…..…………………………………………….48
3.4 熱分析 ………………………………………………………………….48
3.4.1 熱差分析（DTA） …………………………………………………..49
3.4.2 示差掃描熱量計（DSC）……………………………………………49
3.4.3 高溫顯微分析……………………………………………………...50
3.5 微硬度分析 …………………………………………………………….50
第四章　結果與討論…………………………………………………………….57
4.1　顯微結構分析 …………………………………………………………..57
4.1.1　X-光繞射分析 ……………………………………………………...58
4.1.2　電子顯微鏡觀察 …………………………………………………...59
4.1.2.1 掃描式電子顯微鏡（SEM）…………………………………….59
4.1.2.2 穿透式電子顯微鏡（TEM）…………………………………….60
4.1.3　Hot stage金相觀察 ………………………………………………63
4.2 熱性質分析………………………………………………………………..63
4.2.1 玻璃形成能力 ……………………………………………………...63
4.2.1.1 玻璃轉換溫度（Tg）與液相線溫度（Tl）相對關係……………64
4.2.1.2 簡化玻璃溫度（Trg）……………………………..………………66
4.2.1.3 玻璃轉換溫度（Tg）與結晶化溫度（Tx）相對關係………………66
4.2.2 熱穩定性 …………………………………………………………...67
4.2.2.1 活化能-Kissinger plot ………………………………….…...68
4.2.2.2 活化能-JMA plot ………………………………………….……69
4.3 結晶動力分析 …………………………………………………………70
4.3.1 恆溫結晶及Avrami Exponent ……………………………….…..71
4.3.2 晶粒成長控制機制………………………………………………….72
4.4　 機械性質分析………………………………………………………..…73
4.4.1 微硬度………………………………………………………………73
4.4.2 破斷面觀察及分析 ………………………………………………..75
第五章 結論 ………………………………………………………………119
參考資料……………………………………………………………………..121

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