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  • 學位論文

藉由鉭、氮添加於鋯-銅-鋁-銀金屬玻璃薄膜 以提升熱及機械特性

Doping of Tantalum and Nitrogen in Zr-Cu-Al-Ag Thin Film Metallic Glass for Improved Thermal and Mechanical Properties

指導教授 : 杜正恭

摘要


金屬玻璃由於具良好機械性質、高表面精度等獨特性質,在諸多前瞻領域深具應用潛力,其中硬度和熱穩定性之提升為各種應用中共通的目標。添加微量元素在金屬玻璃中為一提升機械與熱性質之有效方法。氮元素由於其高電負度與小原子半徑,預期會對金屬玻璃性質造成極為顯著影響。 本研究中,藉由氮原子添加於鋯銅鋁銀金屬中發展出一新金屬玻璃系譜。從Tg和彈性模數趨勢可看出氮原子之添加可使玻璃態自由能降低。當氮添加濃度增高時,會形成更多以氮原子為中心之團簇,更難被塑性變形。藉由氮添加,起始結晶溫度(Tx)比起一般鋯基金屬玻璃來得高出許多,顯示該非晶態擁有更低位能。先在鋯銅鋁銀中引入鉭原子,可藉由氮化鉭結晶態之競爭使氮化鋯之結晶態較不穩定,最終使氮元素在鉭鋯銅鋁銀金屬玻璃薄膜中的非晶成份區間變寬。氮添加之鉭鋯銅鋁銀金屬玻璃薄膜硬度可超過10 GPa、Tg接近800 K、過冷液態區間 (supercool liquid region) 寬達112 K,在鋯基金屬玻璃中展現優異的熱及機械性質。

並列摘要


Owing to the unique properties, such as excellent mechanical performance, and nano-scale surface roughness, metallic glass can be applied in various novel fields. Meanwhile, the improvement of thermal stability and hardness is the common target in these applications. Minor alloying is an effective method to enhance the thermal and mechanical properties of metallic glasses. Different from elements used to be doped into metallic glass, the role nitrogen atoms play in metallic glass is quite distinct and critically important, owing to its strong electronegativity and small atomic radius. In this work, an alternative class of metallic glass is developed. By adding nitrogen into Zr-Cu-Al-Ag TFMG, the configuration energy of short range structure is greatly modified. From the viewpoint of thermal behavior, the evolution of Tg and elastic modulus with nitrogen could be well correlated, implying significant effect of nitrogen atoms on the potential energy landscape (PEL) of the TFMGs. Besides, more amounts of nitrogen addition lead to the increase of short range order structure in the amorphous matrix. That is, most metallic atoms are strongly attracted by nitrogen, forming the nitrogen-centered cluster, in which more energy is required to cause plastic deformation. On the other hand, a meta-stable state with lower energy is attained as indicated by the much higher Tx than normal Zr-based metallic glasses. However, the amorphicity region of nitrogen in Zr-Cu-Al-Ag metallic glass is not wide enough, restricting the enhancement amount of thermal and mechanical performances. By incorporating Ta firstly, the competing ZrN crystalline phase is destabilized, leading to the wider amorphicity region of nitrogen in Ta-Zr-Cu-Al-Ag TFMG. As a result, hardness over 10 GPa, Tg near 800 K, and supercool liquid region as wide as 112K is achieved in the nitrogen-doped Ta-Zr-Cu-Al-Ag TFMG.

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