藉由製程溫度控制鍍製鋯-銅-鎳-鋁金屬玻璃薄膜及其微結構、熱、機械與抗菌性質

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研究生：	朱嘉鴻 Chu, Jia-Hong
論文名稱：	藉由製程溫度控制鍍製鋯-銅-鎳-鋁金屬玻璃薄膜及其微結構、熱、機械與抗菌性質 Microstructure, Thermal, Mechanical and Antimicrobial Properties in Zr-Cu-Ni-Al Thin Film Metallic Glass via Processing Temperature Control
指導教授：	杜正恭 Duh, Jenq-Gong
口試委員:	朱瑾李志偉
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學工程學系 Materials Science and Engineering
論文出版年：	2013
畢業學年度：	101
語文別：	英文
論文頁數：	95
中文關鍵詞：	金屬玻璃薄膜、濺鍍、熱性質、機械性質、抗菌性質
相關次數：	點閱：2 下載：0
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鋯基金屬玻璃薄膜具有良好的玻璃形成能力(GFA)、抗腐蝕以及生物相容性等獨特性質，在許多領域深具潛在的應用發展。利用濺鍍技術可鍍製超光滑表面之金屬玻璃薄膜，有利於對不鏽鋼製品上進行表面改質，並可進一步擴展到醫療器具等用途。在生醫領域的應用與微機電系統中薄膜是很常被使用的材料，因此提升金屬玻璃薄膜之機械性質及多功能性是必要的。
本實驗試以製程溫度控制，濺鍍具有抗菌效果之金屬玻璃薄膜於304不鏽鋼片上，探討基板溫度增加對於薄膜性質上的影響。由於濺鍍過程中具有非常快的冷卻速度而鋯基金屬玻璃具有優異的玻璃形成能力，在經由不同溫度下製程的薄膜，對於非晶質基底結構並無明顯影響，所有的薄膜表現出相似的結構和熱性質。藉由機械性質的量測，其硬度值和楊氏模數可提高到7.1 GPa及135 GPa，遠高於室溫製程時的4.7 GPa和109 GPa，可歸功於製程溫度增加所造成平均原子距離的縮短、短程有序原子團簇的增加與自由體積的減少。
另一方面，透過液態培養法及平板計數法進行金屬玻璃薄膜抗菌性能測試，參照日本工業標準(JIS standard)，在大腸桿菌及金黃葡萄球菌的檢驗中，其薄膜抗菌率高達99%。由於非晶質薄膜具有原子級平整表面、疏水性和釋放銅離子能力，結果顯示304不鏽鋼基材上披覆一層金屬玻璃薄膜時，其呈現顯著的抗菌能力，除此之外，金屬玻璃薄膜與細菌之間的相互作用現象也更進一步討論。故藉由製程溫度的控制對於薄膜機械性質上能有顯著的提升，同時具有良好的抗菌能力，期望藉由本研究可以將金屬玻璃薄膜進一步推廣至醫療器具的應用，同時也降低院內感染的可能性。

Zr-based thin film metallic glass (TFMG) exhibiting the unique properties of good glass forming ability (GFA), corrosion resistance, and biocompatibility can be applied in various novel fields of industries. In addition, an ultra smooth surface is obtained with the TFMG coatings, which is beneficial to modify the surface condition of stainless steel and can be extended to medical appliances such as surgical blades and micro-surgery scissors. Since the thin film materials are customarily employed to biomedical applications and micro-electro-mechanical system (MEMS), the improvement of mechanical properties and functionality of thin film metallic glass is imperative.
The aims of this study are to fabricate the antimicrobial TFMG coatings onto SUS304 plates and to investigate the characteristics of coatings with various substrate temperatures. The amorphous matrix and cluster structure are slightly affected by the processing temperatures due to high cooling rate during deposition and superior glass-forming ability (GFA). All the coatings exhibit similar structural and thermal properties, yet the hardness and elastic modulus can significantly increase to 7.1 GPa and 135 GPa, respectively, with increasing the processing temperature up to 400 oC, well above the values of 4.7 GPa and 109 GPa at room temperature. The enhancement of mechanical properties are attributed to the shortening of average atomic distance, the increase of the short range ordered clusters and the vanish of free volumes. Liquid culture methods and plate counting methods are used to assess the antimicrobial performance of specimens. The antimicrobial rate against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) under JIS standard is over 99%. The results show that the surface of SUS 304 stainless steel substrate can be modified with deposited Zr-Cu-Ni-Al TFMG, and their improved antimicrobial efficacy against those bacteria is attributed to their amorphous rough surface, hydrophobic properties and released copper ion. In addition, the phenomenon of interaction between TFMG and bacteria has also been discussed. The TFMG developed in this study with adequate hardness, good glass forming ability and antimicrobial efficiencies can be used as a promising candidate to improve the surface properties of the medical appliances and also to reduce the possibility of nosocomial infection.

Table List……………………………………………………………………………………………………………………………III
Figure Caption……………………………………………………………………………………………………………………IV
Abstract………………………………………………………………………………………………………………………………………V
Chapter 1 Introduction…………………………………………………………………………………………………1
1    Background……………………………………………………………………………………………………………1
2    Thin film metallic glass (TFMG)……………………………………………………1
3    Motivation and objectives……………………………………………………………………2
Chapter 2 Literature Review……………………………………………………………………………………6
1    Bulk Metallic Glass (BMG)……………………………………………………………………6
1.1    Development of metallic glass…………………………………………………………6
1.2    Glass-forming ability (GFA)………………………………………………………………9
1.3    Physical and mechanical properties of MG…………………………12
2    Atomic structure of metallic glass…………………………………………15
2.1    Short Range Order………………………………………………………………………………………17
2.2    Free volume………………………………………………………………………………………………………20
3    Zr-Cu-Ni-Al metallic glass………………………………………………………………22
3.1    Zr/Cu-based metallic glass………………………………………………………………22
3.2    Effect of Al addition into Zr-Cu metallic glass………24
3.3    Effect of Ni addition into Zr-Cu-Al metallic glass    …………………………………………………………………………………………………………………………………………………………28
4    Physical vapor deposition (PVD)…………………………………………………29
4.1    Sputtering technique………………………………………………………………………………29
4.2    DC sputtering…………………………………………………………………………………………………30
5    Thin film metallic glass (TFMG)…………………………………………………33
5.1    Thermal stability………………………………………………………………………………………34
5.2    Mechanical properties……………………………………………………………………………37
6    Importance and antimicrobial application of thin film coatings………………………………………………………………………………………………………………………39
6.1    304 stainless steel…………………………………………………………………………………40
6.2    Antimicrobial ability improvement with coatings………42
Chapter 3 Experiment Procedure…………………………………………………………………………44
1    Target and substrate preparation………………………………………………44
1.1    Target preparation……………………………………………………………………………………44
1.2    Sample cutting………………………………………………………………………………………………45
1.3    Ultrasonic cleaning…………………………………………………………………………………45
2    Sputtering deposition……………………………………………………………………………47
2.1    Fabrication of Zr-Cu-Ni-Al TFMG…………………………………………………47
3    Measurement and analysis……………………………………………………………………49
3.1    Composition analysis………………………………………………………………………………49
3.2    Phase identification………………………………………………………………………………49
3.3    Surface characterization……………………………………………………………………50
3.4    Microstructure analysis………………………………………………………………………50
3.5    Nanohardness and elastic modulus………………………………………………51
3.6    Differential scanning calorimeter analysis……………………51
4    Evaluation of antimicrobial activity……………………………………53
4.1    Antimicrobial test……………………………………………………………………………………53
4.2    Copper ion release test………………………………………………………………………54
4.3    Surface physical properties……………………………………………………………54
Chapter 4 Results and Discussions…………………………………………………………………57
1    Fabrication of Zr-Cu-Ni-Al TFMG coatings…………………………57
1.1    Composition evaluation…………………………………………………………………………57
1.2    Structure identification……………………………………………………………………57
1.3    Microstructure analysis………………………………………………………………………58
2    Structure, thermal behavior, and mechanical properties of Zr-Cu-Ni-Al TFMG coatings…………………………………………………64
2.1    Thermal properties……………………………………………………………………………………64
2.2    Mechanical properties and microstructure…………………………65
3    Antimicrobial activity evaluation of Zr-Cu-Ni-Al TFMG coatings………………………………………………………………………………………………………………………73
3.1    Surface physical properties……………………………………………………………73
3.2    Antimicrobial efficacy…………………………………………………………………………74
3.3    Immersion tests……………………………………………………………………………………………75
3.4    Antimicrobial mechanism………………………………………………………………………76
Chapter 5 Conclusions…………………………………………………………………………………………………86
References………………………………………………………………………………………………………………………………88



                                

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