臺灣博碩士論文加值系統

本研究中採用陰極電弧蒸鍍技術(CAE)，搭配鋁鉻(AlCr)、鋁鉻硼(AlCrB)、鈦鋁鈮(TiAlNb)、鈦鋁鈮矽(TiAlNbSi)，沉積氮化鋁鉻(AlCrN)、氮化鋁鉻硼(AlCrBN)、氮化鈦鋁鈮(TiAlNbN)及氮化鈦鋁鈮矽(TiAlNbSiN)薄膜。同時利用兩個靶材共鍍AlCrN/TiAlNbN與AlCrBN/TiAlNbSiN多元多層氮化物薄膜，再針對AlCrB及TiAlNbSi靶電流進行優化，調整薄膜元素原子比例以提升薄膜高溫性質。接著進行真空退火(800、900、1000 ℃)與氧化退火(900 ℃)，針對薄膜多層薄膜的微結構、機械性質進行探討。最後在碳化鎢刀具上鍍製多層膜，以測試多元多層合金氮化物薄膜應用於刀具鍍膜的可行性。
本研究使用場發射掃描式電子顯微鏡(FE-SEM)與場發射穿透式電子顯微鏡(FE-TEM)觀察薄膜橫截面微結構；使用場發射電子微探儀(EPMA)進行薄膜元素成分分析；利用低掠角薄膜X光繞射儀(GIXRD)分析薄膜晶體結構與結晶相分析。機械性質分析先以洛式壓痕試驗機評估薄膜與基材之間的附著力，再利用奈米壓痕試驗機與球對盤磨耗試驗機量測薄膜機械性質(硬度和彈性係數)與抗磨耗性能。對於薄膜的高溫抗氧化性質實驗，利用二次離子質譜儀(TOF-SIMS)與化學分析電子光譜儀(ESCA)針對薄膜氧化層進行分析，探討氧化層生長機制。最後將AlCrN/TiAlNbN、AlCrBN/TiAlNbSiN薄膜鍍製於碳化鎢端銑刀，對SUS304不銹鋼進行循環切削測試，以乾式與濕式切削探討薄膜對於刀具壽命的影響。
根據研究結果顯示AlCrBN/TiAlNbSiN系列薄膜相較於AlCrN/TiAlNbN薄膜，因矽與硼的添加導致晶粒細化抑制晶粒成長，形成緻密的奈米複合膜結構，同時受到奈米多層膜的強化機制使其獲得高硬度(34.8 GPa)與低磨耗率(4.65x10-7 mm3/Nm)。在高溫真空退火後，AlCrBN/TiAlNbSiN薄膜仍保有34 GPa高硬度而具有熱穩定性。
在900 ℃大氣氧化一小時後，AlCrBN/TiAlNbSiN薄膜中的奈米晶複合結構可以阻礙氧原子藉由晶界進入薄膜內部，且Al2O3、Cr2O3和SiO2氧化物的產生延緩氧原子擴散至薄膜內層的速率，使其氧化層僅有83 nm。根據切削實驗結果得知，適當成分配比之AlCrBN/TiAlNbSiN鍍膜刀具的磨耗量最少具有最佳的抗磨耗性能與球對盤磨耗試驗結果相符。因薄膜在高溫條件下仍保有高硬度與高溫抗氧化能力，使其在加工不銹鋼時能夠減少刀具磨耗，保持刀腹平整與均勻磨耗。相較於未鍍膜刀具，在濕式切削的條件下能夠有效提升刀具壽命566%，在乾式切削下能夠使刀具壽命提升300%、磨損量下降44%。

In this study, cathodic arc evaporation (CAE) was used to deposit AlCrN, AlCrBN, TiAlNbN and TiAlNbSiN hard coatings using AlCr, AlCrB, TiAlNb, TiAlNbSi targets. Multilayered coatings of AlCrN/TiAlNbN and AlCrBN/TiAlNbSiN were also deposited. By controlling the cathode currents of AlCrB and TiAlNbSi targets, the atomic ratio of the AlCrBN/TiAlNbSiN were adjusted. Vacuum annealing (800, 900, 1000 ℃) and high-temperature oxidation at 900 ℃ were carried out to study the thermal stabilities and oxidation resistance of the coatings. Finally, the coatings were deposited on tungsten carbide end mills for cutting tests of SUS 304 materials.
In this study, Field Emission Scanning Electron Microscope (FE-SEM) and Field Emission Transmission Electron Microscope (FE-TEM) were used to observe the cross-sectional microstructure of the deposited coatings. Electron Probe Microanalyzer (EPMA) was used for the elemental composition analysis of the coatings. Grazing incidence X-Ray diffraction (GIXRD) was used for crystal structure and crystal phase analyses. A Rockwell indentation tester was used to evaluate the adhesion between the coating and the substrate. Nanoindentation was used to measure the hardness and elastic modulus of the coatings. A ball on the disc tribometer was used to study the tribological characteristics and wear resistance. For the high-temperature oxidation resistance analyses, Secondary ion mass spectrometry (SIMS) and Electron Spectroscopy for Chemical Analyses (ESCA) were used to analyze the oxide scale to explore the growth mechanism of the oxide layer. Finally, AlCrN/TiAlNbN and AlCrBN/TiAlNbSiN films were deposited on tungsten carbide end mills, and cyclic cutting tests were carried out on SUS304 stainless steel using a CNC milling machine, and the influence of the hard coatings on tool life was discussed.
Compared to the AlCrN/TiAlNbN, the AlCrBN/TiAlNbSiN series coatings, showed a grain refinement effect due to the addition of silicon and boron, which inhibited the grain growth. formed a dense nanocomposite structure was obtained and strengthened by the multilayers in nanometer range. High hardness (34.8 GPa) and low wear rate (4.65 x 10-7 mm3/Nm) were obtained for the AlCrBN/TiAlNbSiN coatings. After annealing at 800 ℃, the AlCrBN/TiAlNbSiN was still maintain high hardness value of 35.2 GPa. The hardness decreased after 900 °C annealing due to grain growth, and no hexagonal AlN generation.
After oxidation at 900 °C, nanocrystals with B and Si in the AlCrBN/TiAlNbSiN coatings prevented oxygen interdiffusion entering the coating through the grain boundary. The oxide layer was only 83 nm. Dense Al2O3, Cr2O3, and SiO2 oxides generated and slowed down the diffusion rate. According to the cutting test results, the wear performance of the AlCrBN/TiAlNbSiN coatings was similar to the ball-to-disk wear test results. Compared to uncoated tools, the tool life of AlCrBN/TiAlNbSiN was effectively increased by 566% under wet cutting condition, and the tool life was increased by 300% under dry cutting condition. The good thermal stabilitiy possessing high hardness at high temperature and oxidation resistance improved the cutting performance of AlCrBN/TiAlNbSiN coated tools.

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. 薄膜強化理論............................................................3
2.1.1 晶粒細化強化（strengthening by grain size reduction ）..................3
2.1.2 固溶強化(solid-solution strengthening)................................4
2.1.3 奈米複合結構強化..........................................................5
2.2. 硬質薄膜................................................................7
2.2.1 氮化鋁鉻................................................................7
2.2.2 氮化鋁鈦................................................................13
2.2.3 多元合金氮化物...........................................................17
2.2.4 高熵合金氮化物...........................................................21
2.3. 難削材加工...............................................................26
2.4. 刀具磨損機制..........................................................31
第三章 實驗方法...............................................................34
3.1. 實驗流程...............................................................34
3.2. 薄膜設計與實驗方法........................................................36
3.2.1 前處理及鍍膜步驟.........................................................36
3.2.2 AlCrN單層薄膜製程設計....................................................38
3.2.3 AlCrBN單層薄膜製程設計................................................39
3.2.4 TiAlNbN單層薄膜製程設計..................................................40
3.2.5 TiAlNbSiN單層薄膜製程設計................................................41
3.2.6 AlTiCrNbN多層多元氮化物薄膜製程設計.......................................42
3.2.7 AlCrBN/TiAlNbSiN奈米複合多層多元氮化物薄膜製程設計.......................43
3.3. 真空退火系統(Vacuum Annealing System)...................................44
3.4. 薄膜微結構與成分分析....................................................46
3.4.1 高解析度場發射掃描式電子顯微鏡(Field Emission Scanning Electron Microscope, FESEM)........................................................................46
3.4.2 場發射穿透式電子顯微鏡(Field Emission Transmission Electron Microscope, FETEM).......................................................................48
3.4.3 化學分析電子能譜儀(Electron Spectroscope for Chemical Analysis, ESCA).........................................................................50
3.4.4 二次離子質譜儀(Secondary Ion Mass Spectrometer, SIMS)....................51
3.4.5 X光繞射分析儀(X-Ray Diffractometer, XRD).........................................................................52
3.4.6 場發射電子微探儀(Field Emission Electron Probe Microanalyzer, EPMA)........................................................................54
3.5. 薄膜機械性質分析.........................................................55
3.5.1 洛式硬度試驗機(Rockwell Hardness)........................................55
3.5.2 奈米壓痕試驗機(Nano-indentation)........................................56
3.5.3 磨耗試驗機(Tribometer).................................................57
3.6. SUS304切削測試..........................................................58
第四章 結果與討論.............................................................60
4.1. 薄膜常溫微結構分析.......................................................60
4.1.1 SEM微結構...............................................................60
4.1.2 EPMA元素成分比例定量分析.................................................62
4.1.3 X光繞射分析............................................................63
4.1.4 多元合金氮化物薄膜之TEM分析..............................................67
4.2. 薄膜常溫機械性質分析......................................................75
4.2.1 洛式壓痕分析............................................................75
4.2.2 奈米壓痕分析............................................................77
4.2.3 磨耗試驗分析.............................................................79
4.3. 真空退火之薄膜熱穩定性分析.................................................82
4.3.1 奈米壓痕分析.............................................................82
4.3.2 X光繞射分析..............................................................84
4.4. 高溫氧化退火後之薄膜微結構分析.............................................90
4.4.1 EPMA元素成分比例定量分析.................................................90
4.4.2 二次離子質譜儀縱深成分分析(SIMS)..........................................91
4.4.3 XPS化學鍵結態與成分分析..................................................97
4.4.4 AlCrBN/TiAlNbSiN薄膜之TEM分析..........................................105
4.5. 不銹鋼切削測試..........................................................110
第五章 結論..................................................................121
5.1. 薄膜微結構分析結論.......................................................121
5.2. 薄膜機械性質分析........................................................122
5.3. 切削性能分析結論.........................................................123
第六章 未來展望.............................................................124
參考文獻....................................................................125
EXTENDED ABSTRACT..........................................................133

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