臺灣博碩士論文加值系統

因前人研究中指出，添加4at.%Si、1at.%B之鋯基非晶質具有高熱穩定性，其結晶活化能高達390kJ/mole，同時鋯基非晶質合金具有寬廣過冷區(~80K)、高玻璃形成能力及良好的機械性質，故本實驗以Zr60Al7.5Ni10Cu17.5Si4B1非晶質合金作為研究主題，藉由示差掃描熱分析儀(DSC)進行等速率升溫與恆溫退火測試及結合穿透式電子顯微鏡(TEM)之解析以深入探討該合金之結晶成核與成長機制。

由實驗之結果顯示，在非恆溫分析法中Zr60Al7.5Ni10Cu17.5Si4B1與Zr65Al7.5Ni10Cu12.5Si4B1之n值皆隨溫度升高而降低，其值介於4~2之間，即表示結晶初期是以三度空間成長，隨溫度與時間的增加，轉變成二度或一度空間成長。且Zr60Al7.5Ni10Cu17.5Si4B1合金晶核飽和點約為88%、Zr65Al7.5Ni10Cu12.5Si4B1合金約為87%、Zr61Al7.5Ni10Cu17.5Si4合金約為64%及Zr65Al7.5Ni10Cu17.5合金約為47%，即表示添加4 at.%矽、1 at.%硼之鋯基非晶質合金中晶核成長所需的能量較高，其熱穩定性較佳。

在XRD及TEM之微結構分析觀察可知，在714K，恆溫退火熱處理後之試片，Zr2Cu結晶相在低溫及結晶初期(<1%結晶率)時最先出現，隨著恆溫退火時間的增加依序有Zr2Ni、Zr3Al及Zr3Al2結晶相的生成(35%結晶率)，當恆溫退火試片達到71%結晶率時除了先前產生之結晶相外，還有ZrNi2Al結晶相的生成，最後，在完全結晶之試片上析出Zr2Si結晶相。

在STEM line scan成分分析上，714K恆溫退火3000秒(71%結晶率)之Zr60Al7.5Ni10Cu17.5Si4B1合金試片，可發現Si會聚集在晶粒邊緣，阻礙了其他原子(Zr、Cu、Al、Ni)之擴散至Zr2Cu晶粒與非晶基地界面，因而阻礙晶粒的成長。在足夠之恆溫退火時間(714K恆溫退火4小時，100%結晶率)後，含量較少之Si元素與Zr產生結合，產生Zr2Si結晶相。

TEM觀察中發現，當Zr60Al7.5Ni10Cu17.5Si4B1合金在714K恆溫退火之試片，Zr2Cu結晶相在低溫及結晶初期(<1%結晶率)時晶粒大小約5nm，隨著退火時間的增加(約71%結晶率)時，Zr2Cu結晶相之晶粒大小可達到約25nm。將晶粒大小計算後可發現，Zr2Cu晶粒大小在三次方時與退火時間呈線性關係，即表示晶粒成長是呈三次元方位。並計算其結晶成長動力學發現其成長活化能約為210±25kJ/mole，高於Zr65Al7.5Ni10Cu17.5合金之晶粒成長活化能(100 ± 10 kJ/mole)， 此結果顯示Si的添加會阻礙Zr2Cu相之成長，使Zr60Al7.5Ni10Cu17.5Si4B1合金成長需要較大之能量，即表示Zr60Al7.5Ni10Cu17.5Si4B1合金擁有熱穩定性較佳。

According to the study of Jang’s group, the Zr60Al7.5Ni10Cu17.5Si4B1 amorphous alloy presents 390 kJ/mole high activation energy of crystallization, relatively wide supercooled liquid region (~ 80 K), high glass forming ability and high hardness. Therefore, the Zr60Al7.5Ni10Cu17.5Si4B1 amorphous alloy was selected to investigate its crystallization kinetics and thermal stability in this study. The crystallization behavior and microstructure development during isothermal annealing were examined by the DSC, X-ray diffractometry and TEM techniques with nano beam capability.

The result of non-isothermal DSC analysis revealed that a decreasing trend of Avrami n values, from 4 to 2, with temperature and crystallization ratio for both of Zr60Al7.5Ni10Cu17.5Si4B1 and Zr65Al7.5Ni10Cu12.5Si4B1 amorphous alloys. This implies that three dimensional crystal growth occurs at the early stage of crystallization, and the crystal growth would change to two or even one dimensional growth as increasing the temperature and crystallization fraction. In addition, the transition point between nucleation and crystal growth occurs at about 88% and 87% crystallization ratio for Zr60Al7.5Ni10Cu17.5Si4B1 and Zr65Al7.5Ni10Cu12.5Si4B1 alloy, respectively. These values are much higher than 64% and 47% crystallization ratio for Zr65Al7.5Ni10Cu17.5Si4 and Zr65Al7.5Ni10Cu17.5 alloy, respectively, and demonstrate the positive effect on improving the thermal stability of Zr based amorphous alloy by adding at.% silicon and 1 at.% boron.

TEM observation of the isothermal annealed Zr60Al7.5Ni10Cu17.5Si4B1 samples at 714 K explored that a sequence of different crystalline phase crystallized from the amorphous matrix step by step. The Zr2Cu crystal was observed at the beginning of isothermal annealing (corresponding to % crystallization). As increasing annealing time, the Zr2Ni, Zr3Al and Zr3Al2 crystals were found at the % crystallization. After then, the ZrNi2Al crystal was observed at 71% crystallization. Finally, the Zr2Si was crystallized after fully crystallization condition.

The line scan analysis of STEM on the Zr60Al7.5Ni10Cu17.5Si4B1 sample (which was isothermally annealed at 714K for 3000s and corresponding to 71% crystallization) revealed that Si atoms segregate around the Zr2Cu crystal, and seem to restrain other atoms (Zr, Al, Ni and Cu) diffusing to the surface of Zr2Cu. This implies that Si atoms would inhibit the grain growth of Zr2Cu crystal. In addition, Si atoms will combine with Zr atoms to form Zr2Si crystal after enough annealing time, i.e. 4 hours isothermal annealing at 714 K (which corresponding to 100% crystallization).

When the Zr60Al7.5 Cu17.5Ni10Si4B1 sample isothermally annealed at 714K, Zr2Cu crystals with average size about 5 nm were first observed at the early stage of 1% crystallization by TEM observation. The Zr2Cu crystal size increases with annealing time then reaches about the average size of 25 nm at the stage of 72% crystallization. Additionally, the grain growth time as a function of the cube of particle size of the Zr2Cu type crystalline phases presented a good linear relationship. This indicates that the crystal growth of the Zr60Al7.5Cu17.5Ni10Si4B1 alloy belongs to thermal activation process. The activation energy for the grain growth of Zr2Cu in the Zr60Al7.5Ni10Cu17.5Si4B1 amorphous alloy is calculated to be 210 ± 25 kJ/mole, further higher than those for the base alloy (100 ± 10 kJ/mole), again demonstrating the higher thermal stability of the Zr60Al7.5Ni10Cu17.5Si4B1 amorphous alloy.

中文摘要…………………………………………………………….....................Ⅰ
英文摘要………………………………………………………………………….Ⅳ
誌謝……………………………………………………………………………….Ⅶ
總目錄…………………………………………………………………….............Ⅷ
表目錄……………………………………………………………………………XI
圖目錄…………………………………………………………………………...XII
第一章 前言……………………………………………………………………...1
第二章 理論基礎………………………………………………………………...3
2-1 非晶質合金發展歷程………………………………………………….3
2-2 實驗歸納法…………………………………………………………….4
2-3 非晶質合金之製造方法……………………………………………….5
2-4 非晶質合金之種類…………………………………………………….6
2-5 非晶質合金之特性…………………………………………………….6
2-5-1 機械性質………………………………………………………7
2-5-2 化學性質-耐蝕性……………………………………………...7
2-5-3 磁性質…………………………………………………………8
2-5-4 其他性質………………………………………………………8
2-6 非晶質合金之相關理論……………………………………………….9
2-6-1 熱力學………………………………………………................9
2-6-2 動力學…………………………………………………………9
2-6-3 結晶觀點……………………………………………………..12
2-7 非晶質合金之熱力學性質………………………………………...…12
2-7-1 非晶質之平衡………………………………………………..12
2-7-2 玻璃轉換溫度Tg……………………………………………..13
2-7-3 玻璃形成能力指標…………………………………………..14
2-7-3-1 簡化玻璃溫度Trg……………..……………………14
2-7-3-2 γ值…………………………………………............15
2-8 熱力學………………………………………………………………...15
2-8-1 恆溫分析法…………………………………………………..15
2-8-2 非恆溫分析法………………………………………………..17
2-8-2-1 一般非恆溫分析法………………………………...17
2-8-2-2 修正之非恆溫分析法……………………………...20
第三章 實驗步驟……………………………………………………….............23
3-1 合金試片配製………………………………………………………...23
3-1-1 合金鑄錠熔製………………………………………………..23
3-1-2 薄帶製作……………………………………………………..24
3-2 熱性質分析…………………………………………………………...24
3-2-1 熱差分析(DTA)……………………………………………...24
3-2-2 示差掃描熱分析(DSC)……………………………………...25
3-2-2-1 等速率升溫………………………………………..25
3-2-2-2 恆溫加熱…………………………………………..25
3-3 微觀組織分析………………..……………………………………….25
3-3-1 X光繞射儀…………………………………………………..25
3-3-2 掃描式電子顯微鏡(SEM)..………………………………….26
3-3-3 穿透式電子顯微鏡(TEM)…………………………………..26
第四章 結果與討論……………………………………………………............27
4-1 熱性質分析…………………………………………………………...27
4-1-1 非恆溫熱力學和動力學分析………………………………..27
4-1-1-1 一般之非恆溫分析法-Kissinger plot……………...28
4-1-1-2 修正之非恆溫分析法……………………………...29
4-1-2 恆溫熱力學和動力學分析…………………………………..30
4-2 微觀結構分析………………………………………………………...31
4-2-1 X光繞射分析………………………………………………...31
4-2-2 TEM觀察及動力學分析…………………………….............32
4-2-3 SEM觀察及破斷面分析………………………...…………..39
第五章 結論…………………………………………………………….............41
參考文獻………………………………………………………………….............96

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