臺灣博碩士論文加值系統

高熵合金是以五種或五種以上的主元素所組成之合金，每種元素原子百分比應介於5%至35%，由於四大效應：高熵效應、嚴重晶格畸變效應、延遲擴散效應與雞尾酒效應的影響，使其可根據組成元素的調配展現各種優異特性。在本研究中採用陰極電弧蒸鍍技術(CAE)，於製程中使用三種不同轉架旋轉速度(1.5、2與4RPM)，搭配鋁鉻矽(AlCrSi)、鈦釩(TiV)、鋯(Zr)三靶共鍍ATZ系列氮化物薄膜；再利用鋁鈦矽(AlTiSi)、鉻釩(CrV)、鋯(Zr)三靶共鍍ACZ系列氮化物薄膜，並另外鍍製AlTiSiCrV與AlCrSiTiV高熵合金薄膜，針對其結構、表面性質與機械性質的變化進行探討。
本研究藉由使用場發射掃描式電子顯微鏡(FE-SEM)與高解析穿透式電子顯微鏡(HR-TEM)觀察並分析薄膜之微結構並搭配X光能量分散光譜分析儀(EDS)測量元素成分，接著利用X光繞射分析儀(XRD)觀察薄膜之晶體結構及結晶相分析，再使用三維表面輪廓儀與水接觸角檢測薄膜的表面特徵。機械性質分析先利用洛氏壓痕試驗機評估薄膜與基材之間的附著性能，接著透過微克氏壓痕試驗機及奈米壓痕試驗機測量薄膜硬度值及彈性係數，並透過球對盤磨耗試驗機(Ball-On-Disk)觀察薄膜抗磨耗性能。最後將薄膜鍍製在微型銑刀，對印刷電路板(PCB)進行乾式循環切削測試，探討薄膜對刀具壽命的影響。
根據FE-SEM對薄膜截面觀察的結果顯示，隨轉架速度增加薄膜的週期厚度皆逐漸下降。透過HR-TEM對薄膜進行更進一步的觀察果顯示，薄膜的奈米多層週期厚度由65奈米下降至約13奈米。由X光繞射分析結果顯示，隨著轉架旋轉速度上升，所有鍍膜樣品繞射峰的數量皆逐漸減少呈現優選方位。薄膜的表面粗糙度測試結果顯示所有氮化物薄膜的粗糙度皆大幅小於高熵合金薄膜，所有樣品的水接觸角皆超過100度，呈現較佳的疏水性能與低表面能。奈米壓痕測試的結果顯示ACZ系列氮化物4RPM與ATZ系列氮化物1.5RPM的樣品同時具有較佳的韌性與較高之硬度，球對盤磨耗500公尺測試中，磨耗率與硬度試驗結果相吻合，硬度較高的樣品具有較佳的抗磨耗性能。最終將表現較佳之薄膜鍍製於刀具上，進行印刷電路板切削測試，結果顯示相較於未鍍刀具，鍍層刀具的磨損下降超過50%。

High-entropy alloys (HEA) were defined as those alloys having at least five major metallic elements each having an atomic percentage between 5% and 35%. Excellent performance can be obtained due to the four factors : high entropy effect, slow diffusion effect, severe lattice distortion and cocktail effect. In this study, a cathodic arc evaporation technology (CAE) was used to deposit AlTiSiCrVZrN HEA nitride coatings. AlCrSi, TiV, Zr targets were adopted to synthesize AlTiSiCrVZrN HEA nitride coatings named ATZ series nitride films; and use AlTiSi, CrV, Zr for the named ACZ series nitride films. Three different substrate rotation speeds (1.5, 2, 4RPM) were used in the process to control the coating structure. Microstructure, surface properties and mechanical properties were discussed.
The microstructure of the deposited coatings was characterized by using a field emission scanning electron microscope (FE-SEM) and a high-resolution transmission electron microscope (HR-TEM) and the chemical composition was measured by an energy dispersive X-ray spectrometer (EDS). X-ray diffraction (XRD) was used to determine the crystal structure and crystalline phase of the films. The surface characteristics of the coaitngs were detected using a three-dimensional surface profile microscopy and water contact angle measurement. A Rockwell indentation tester was used to evaluate the adhesion strength between the coating and the substrate. The coating hardness value and the Young's modulus were measured by nanoindentation. In addition, to study the tribological performance, a ball on disk tribometer was used to evaluate the coating's wear resistance. For the field test of cutting, printed circuit board was machined by the coated micro end mills using a milling machine.
The results of HRTEM and FESEM revealed that the ATZ and ACZ series HEA nitride coatings had a multilayer structure. The periodic thickness of the film decreased from 65 nm to approximately 13 nm for the coatings deposited with 1.5 rpm and 4 rpm, respectively. X-ray diffraction analyses showed that a trend of preferred orientation was found when the rotation speed increased. As compared to the HEA coatings, the surface roughness of ATZ and ACZ
iii
series HEA nitride coatings decreased significantly. The water contact angles of all coatings were higher than 100o, showing better hydrophobicity and low surface energy. The results of the nanoindentation test showed that the ACZ series nitride coating deposited with 4 rpm and ATZ series nitride coating deposited with 1.5 rpm had higher H/E* value and had higher resistance to plastic deformation. The higher H/E value, the better wear resistance was obtained. Finally, the coaitngs were deposited on the end mills, and the cutting test of printed circuit board was performed.

摘要 ............................................................................................................................................. i
Abstract ....................................................................................................................................... ii
誌謝 ........................................................................................................................................... iv
目錄 ............................................................................................................................................ v
表目錄 ..................................................................................................................................... viii
圖目錄 ....................................................................................................................................... ix
第一章 緒論 .............................................................................................................................. 1
1.1 前言 ................................................................................................................................. 1
1.2 研究動機與目的 ............................................................................................................. 2
第二章 文獻回顧 ...................................................................................................................... 3
2.1 氮化物薄膜 ..................................................................................................................... 3
2.1.1 氮化鋁鈦矽(AlTiSiN) .......................................................................................... 3
2.1.2 氮化鋁鉻矽(AlCrSiN) ......................................................................................... 5
2.1.3 氮化鉻釩與氮化鈦釩(CrVN and TiVN) ............................................................. 7
2.1.4 氮化鋯(ZrN) ....................................................................................................... 10
2.2 高熵合金 ....................................................................................................................... 12
2.2.1 高熵合金的發展與定義 .................................................................................... 12
2.2.2 高熵合金的四種強化理論 ................................................................................ 14
2.2.3 氮化物高熵合金薄膜概況 ................................................................................ 17
2.3印刷電路板 .................................................................................................................... 19
2.3.1 印刷電路板的加工 ............................................................................................ 19
2.3.2 印刷電路板銑削加工 ........................................................................................ 20
第三章 實驗方法 .................................................................................................................... 23
3.1 實驗流程 ....................................................................................................................... 23
3.2 薄膜設計與實驗方法 ................................................................................................... 24
3.2.1 前處理及鍍膜步驟 ............................................................................................ 24
3.2.2薄膜製程設計 ..................................................................................................... 26
3.2.3 ACZ系列AlTiSiCrVZr高熵合金及其氮化物薄膜製程設計 ......................... 26
3.2.4 ATZ系列AlCrSiTiVZr高熵合金及其氮化物薄膜製程設計 ......................... 27
3.3 薄膜微結構分析 ........................................................................................................... 28
3.3.1 場發射掃描式電子顯微鏡(Field Emission Scanning Electron Microscope, FE-SEM) ............................................................................................................................. 28
3.3.2 X光繞射分析儀(X-Ray Diffractometer, XRD) ................................................. 30
3.3.3 穿透式電子顯微鏡(Transmission Electron Microscope, TEM) ....................... 32
3.4 薄膜表面性質分析 ....................................................................................................... 34
3.4.1 三維表面輪廓儀(3D-Surface Profiler) .............................................................. 34
3.4.2 水接觸角試驗機(Contact Angle Meter) ............................................................ 35
3.5 薄膜機械性質分析 ....................................................................................................... 36
3.5.1 洛氏硬度試驗機(Rockwell Hardness) .............................................................. 36
3.5.2 微小維克氏硬度試驗(Micro Vickers Hardness Test) ....................................... 38
3.5.3 奈米壓痕試驗(Nano-indentation) ...................................................................... 39
3.5.4 球對盤磨耗試驗(Ball-on-Disc Wear Test) ....................................................... 40
3.6 印刷電路板切削測試 ................................................................................................... 41
3.6.1 印刷電路板 ........................................................................................................ 41
3.6.2 加工機台與切削方式 ........................................................................................ 42
第四章 結果與討論 ................................................................................................................ 45
4.1 薄膜微結構分析 ........................................................................................................... 45
4.1.1 SEM微結構及EDS元素成分分析 ................................................................... 45
4.1.2 X光繞射分析 ..................................................................................................... 51
4.1.3 ACZN4與ACZN1.5之TEM微結構分析 ....................................................... 53
4.2 薄膜表面性質分析 ....................................................................................................... 59
4.2.1 表面形貌分析 .................................................................................................... 59
4.2.1 水接觸角分析 .................................................................................................... 61
4.2 薄膜機械性質分析 ....................................................................................................... 63
4.2.1 洛氏壓痕分析 .................................................................................................... 63
4.2.2 微小維克氏硬度分析 ........................................................................................ 64
4.2.3 奈米壓痕分析 .................................................................................................... 65
4.2.4球對盤磨耗試驗分析 ......................................................................................... 67
4.5 切削電路板測試 ........................................................................................................... 71
第五章 結論 ............................................................................................................................ 74
參考文獻 .................................................................................................................................. 76
Extended Abstract..................................................................................................................... 82

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