臺灣博碩士論文加值系統

過渡金屬氮化物硬質薄膜目前已廣泛在各業使用，如AlTiN、AlCrN、ZrN及AlTiCrN等氮化物薄膜，以上薄膜皆具備高硬度、高強度、耐磨耗及熱穩定性等優異機械性質，其中Cr元素的添加能賦予薄膜延展性及耐磨性，以上所提薄膜已被作為切削和成形工具的保護性薄膜。本論文使用陰極電弧蒸鍍系統(CAE)並利用鋁鈦(AlTi)靶 、純鉻(Cr)靶及純鋯(Zr)靶鍍製多元AlTiZrN薄膜及調整不同鉻靶電流之多元AlTiCrZrN薄膜，更進一步探討鋁、鈦、鉻與鋯元素含量的改變對機械性質之影響。使用氮化鉻(CrN)薄膜作為底層，使附著能力提升，接著利用AlTiCrN作為過渡層，目的為降低薄膜之殘留應力與提升薄膜之機械性質，最後鍍製頂層薄膜。
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、結晶相分析及殘留應力，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與刮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。最後將薄膜鍍製於微型銑刀，對印刷電路板(PCB)進行乾式循環切削測試，並針對薄膜對刀具磨損機制、刀具切削品質及刀具使用壽命進行探討。
根據實驗結果顯示薄膜皆為B1-NaCl結構，且利用SEM觀察薄膜截面，可以發現柱狀晶的成長無中斷，故薄膜於洛氏壓痕試驗及刮痕試驗結果表現附著力良好。透過HR-TEM觀察多層薄膜結構顯示Al14Ti9Zr29N薄膜週期厚度為31.9nm而Al12Ti7Cr12Zr22N薄膜與Al8Ti5Cr21Zr17N薄膜分別為36.4nm與44.5nm。在TEM高倍率圖像傅立葉轉換分析結果中得知Al14Ti9Zr29N薄膜晶相結構主要分為ZrN相及AlTiN相結構，而Al12Ti7Cr12Zr22N與Al8Ti5Cr21Zr17N薄膜晶相結構主要為ZrN相及AlTiCrN相結構，其結果與XRD分析相呼應。奈米壓痕薄膜硬度結果顯示Al14Ti9Zr29N表現最為亮眼，主要為ZrN的貢獻，其硬度約為30.36±3.9(GPa)，而Al12Ti7Cr12Zr22N與Al8Ti5Cr21Zr17N薄膜硬度分別為30.21±1.3(GPa)與28.78±2.8(GPa)，其硬度結果趨勢與鉻(Cr)含量及週期厚度呈反比。殘留應力分析結果顯示，因介層優化設計(介層AlTiCrN)，Al12Ti7Cr12Zr22N薄膜擁有最低之殘留應力(-1.59GPa)，於薄膜親疏水性能分析中，水接觸角均大於100度，呈現較佳的疏水性能與低表面能，與後續刀具切削抗沾黏性能結果相符。球對盤磨耗500公尺測試中，Al14Ti9Zr29N薄膜有最高之磨耗量(4.96x10-6mm3/Nm)，添加Cr元素之Al12Ti7Cr12Zr22N薄膜皆擁有較低之磨耗量(4.21x10-7mm3/Nm)。最後於切削性能方面結果顯示，ZrN、Al14Ti9Zr29N、Al12Ti7Cr12Zr22N與Al8Ti5Cr21Zr17N薄膜刀具與未鍍層刀具比皆擁有較低之刀刃磨耗，而刀具之主要磨耗機制包含黏著磨耗、磨粒磨耗與氧化磨耗等，其中Al14Ti9Zr29N、Al12Ti7Cr12Zr22N與Al8Ti5Cr21Zr17N薄膜刀具與傳統之ZrN磨耗量相比下降約54%，因為多層膜結構具備較佳之薄膜硬度與耐磨性。接著Al12Ti7Cr12Zr22¬N薄膜刀具與未鍍層刀具於切削距離20m比較，刀具磨耗量下降達90%。分析印刷電路板(PCB)切屑毛刺沾黏情形發現含有Cr元素之Al12Ti7Cr12Zr22N、Al8Ti5Cr21Zr17N薄膜刀具與Al14Ti9Zr29N薄膜刀具相比沾黏情況較少，其原因為切削過程為氧化磨損機制，而添加Cr元素之薄膜由於產生氧化物能降低剪切力、潤滑表面並能使刀具與PCB的沾黏行為降低。

Transition metal nitride hard coatings have been widely used in industries, such as AlTiN, AlCrN, ZrN and AlTiCrN. These coatings all have excellent mechanical properties such as high hardness, high strength, wear resistance and thermal stability. The addition of Cr element can give the coatings ductility and wear resistance. The coatings mentioned above have been used as protective coatings for cutting and forming tools. In this paper, multilayered AlTiZrN coatings and multilayered AlTiCrZrN coatings with different Cr target current prepared by cathodic arc evaporation (CAE) system with AlTi target, Cr target and Zr target. The effects of Al, Ti, Cr and Zr contents on mechanical properties were further investigated. Chromium nitride (CrN) coatings was used as the bottom layer to improve the adhesion ability. Then AlTiCrN was used as the transition layer to reduce the residual stress and improve the mechanical properties of the coatings. Finally, the top layer was coated.
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 characterize the microstructure, phase identification and residual stress. The surface characteristics of the coaitngs were detected using a three-dimensional surface profile microscopy and water contact angle measurement. A Rockwell indentation tester and Scratch tester were 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 (PCB) was machined by the coated micro end mills using a milling machine.
According to the experimental results, the coatings are all B1 NaCl structure, and the growth of columnar crystal is uninterrupted by SEM observation of the coatings cross section. Therefore, the adhesion of the coatings is good in the results of Rockwell indentation test and scratch test. The results of Fourier transform analysis of TEM high-power image show that the crystal structure of AlTiZrN coatings is mainly divided into ZrN phase and AlTiN phase, However, the crystal structure of AlTiCrZrN coating is mainly ZrN and AlTiCrN, which is consistent with XRD analysis. The results show that the hardness of Al14Ti9Zr29N is the best, mainly due to the contribution of ZrN, which is about 30.36 ± 3.9 (GPa), while the hardness of Al12Ti7Cr12Zr22N and Al8Ti5Cr21Zr17N coatings are 30.21 ± 1.3 (GPa) and 28.78 ± 2.8 (GPa) respectively. The hardness trend of Al12Ti7Cr12Zr22N and Al8Ti5Cr21Zr17N coatings are inversely proportional to Cr content and the average thickness of the modulation period (λ) .The results of residual stress show that due to the optimized design of the transition layer (AlTiCrN), the Al12Ti7Cr12Zr22N coatings have lower residual stress (-1.59GPa). In the analysis of the hydrophilic and hydrophobic properties of the coatings, the water contact angle is greater than 100 degrees, showing better hydrophobic properties and low surface energy. For the ball-on-disc wear tests of 500meters, Al14Ti9Zr29N coating has the highest wear (4.96x10-6mm3 / nm), and Al12Ti7Cr12Zr22N coating with Cr element has lower wear (4.21x10-7mm3 / nm).Finally, the results of cutting performance show that ZrN, Al14Ti9Zr29N, Al12Ti7Cr12Zr22N and Al8Ti5Cr21Zr17N coated tools have lower flank wear than uncoated tools, and the main wear mechanisms include adhesive wear, abrasive wear and oxidation wear The wear loss of Al12Ti7Cr12Zr22N and Al8Ti5Cr21Zr17N coated tools is about 54% lower than that of traditional ZrN, because the multilayer structure has better hardness and wear resistance. Then, the tool wear of Al12Ti7Cr12Zr22N coated tool is reduced by 90% compared with the uncoated tool at the cutting distance of 20m. It is found that the adhesion of Al12Ti7Cr12Zr22N and Al8Ti5Cr21Zr17N coated tools containing Cr element is less than that of Al14Ti9Zr29N coated tools. The reason is that the cutting process is an oxidation wear mechanism, and the coatings with Cr element can reduce the shear force, lubricate the surface and reduce the adhesion behavior between the tool and PCB.

摘要..................................................i
Abstract................................................iii
誌謝......................................................v
目錄......................................................vi
表目錄....................................ix
圖目錄..........................................x
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 陰極電弧蒸鍍系統...................................................3
2.1.1 原理及特性...................................................3
2.1.2 陰極電弧蒸鍍特點...................................................4
2.1.3 陰極電弧微粒的生成及改善..............................................6
2.2 薄膜成長機制...................................................8
2.3 薄膜結構...................................................10
2.4 硬質薄膜磨潤機制...................................................12
2.4.1 磨潤機制種類...................................................12
2.5 氮化物薄膜介紹...................................................15
2.5.1 氮化鋁鈦(AlTiN)...................................................15
2.5.2 氮化鉻(CrN)...................................................20
2.5.3 氮化鉻鋯(CrZrN)...................................................25
2.5.4 氮化鋯(ZrN)...................................................27
2.5.5 氮化鋁鈦鉻(AlTiCrN)................................................29
2.6 印刷電路板...................................................32
2.6.1 印刷電路板的加工...................................................32
2.6.2 印刷電路板切削...................................................33
第三章 實驗方法...................................................35
3.1 實驗流程...................................................35
3.2 薄膜設計與實驗方法...................................................36
3.2.1 前處理及鍍膜步驟...................................................36
3.3新型電漿增強電磁控弧源...................................................40
3.4薄膜微結構與成分分析...................................................41
3.4.1高解析度場發射掃描式電子顯微鏡(Field Emission Scanning Electron Microscope, FESEM)...................................................41
3.4.2 X光繞射分析儀(X-Ray Diffractometer, XRD)......................42
3.4.3場發射穿透式燈絲電子顯微鏡(Field Emission Transmission Electron Microscope, FETEM)...................................................45
3.5 薄膜表面性質分析...................................................47
3.5.1 三維表面輪廓儀(3D Surface Profilometer).......................47
3.5.2 水接觸角量測儀(Water Contact Angle, WCA)..........................48
3.5 薄膜機械性質分析...................................................50
3.5.1 洛氏硬度試驗機(Rockwell Hardness)...................................50
3.5.2 刮痕試驗機(Scratch tester)...................................52
3.5.3 微小維克氏硬度試驗(Micro Vickers Hardness Test)....................54
3.5.4 奈米壓痕試驗(Nano-indentation)...............................55
3.5.5 球對盤磨耗試驗(Ball-on-Disc Wear Test)...............................56
3.6 印刷電路板切削測試...................................................57
3.6.1 印刷電路板...................................................57
3.6.2 加工機台與切削方式...................................................59
第四章 結果與討論...................................................61
4.1 薄膜微結構分析與成分分析...............................................61
4.1.1 SEM薄膜表面與成分分析.........................................61
4.1.2 X光繞射分析...................................................63
4.1.3TEM薄膜微結構分析..................................................66
4.2 薄膜表面性質分析...................................................75
4.2.1 表面形貌分析...................................................75
4.2.1 水接觸角分析...................................................77
4.3 薄膜機械性質分析...................................................79
4.3.1 洛氏壓痕分析...................................................79
4.3.2 刮痕試驗分析...................................................80
4.3.3薄膜殘留應力分析...................................................82
4.3.4 微小維克氏硬度分析...................................................84
4.3.5奈米壓痕分析...................................................85
4.3.6球對盤磨耗試驗分析...................................................87
4.4 切削電路板分析...................................................92
第五章 結論...................................................101
5.1 薄膜微結構分析結論...................................................101
5.2薄膜表面性質分析結論...................................................102
5.3薄膜機械性質分析結論...................................................102
5.4切削性能分析結論...................................................103
5.5總結...................................................104
第六章 未來展望...................................................105
參考文獻...................................................106
Extended Abstract...................................................115

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