本實驗為貼近切削工業實際工作情形，選用 WC-10 % Co 為基板，並以真空電弧熔煉製備之 AlCrNbSiTi 高熵合金為靶材，使用反應式直流磁控濺鍍法配合氬氣流量的調整以及氮氣閥門的開關，在 400oC 、 0 及 -100 V 環境下鍍製 AlCrNbSiTi 合金層與 (AlCrNbSiTi)50N50 氮化層交替堆疊之多層膜，藉由改變多層膜層數探討多層化對微結構、硬度、附著性及韌性的影響。隨後將多層膜在 900oC 下大氣退火 2 hr 以瞭解其抗氧化與熱穩定性質。最後選擇綜合表現最佳的多層膜鍍覆於 WC-Co 三角形銑刀片上對 304 不鏽鋼做銑削測試，並與商用 TiN 及 TiAlN 做比較。
實驗結果發現在 -100 V 偏壓下鍍製之 200 層膜 W1-200N 擁有最佳的綜合性質，W1-200N 週期 Ʌ 為 11.2 nm，硬度 31.2 GPa已經超越合金膜與氮化膜的硬度平均 (39 + 12.6)/2 GPa，彈性模數亦提高至 487 GPa 超過氮化膜的 453 GPa，出現超模數現象，代表需要更大的應力才能使 W1-200N 產生彈性變形，W1-200N薄膜斷面呈現階梯與波浪狀的形貌說明多層設計能有效使裂縫前進時受到界面阻礙而偏折提高薄膜韌性，HRC 附著性測試也指出 W1-200N 附著性落在最好的 HF1 等級，此外，將經過 900oC 大氣退火兩小時的 S1-200N 製成 TEM 試片，確認氧化層厚度約 130 nm，且界面未發生擴散 (interdiffusion) 現象，具備良好抗氧化性與熱穩定性。在 W1-200N 中，界面產生的外延強化效果已經非常明顯，薄膜突破材料本質特性極限，得到比單層膜更突出的性質。WC-Co 三角形銑刀片上鍍200層膜（I1-200N）銑削結果刀腹磨耗長度 340 μm 比未鍍膜銑刀片、商用單層TiN、TiAlN 以及(AlCrNbSiTi)50N50氮化膜都短，且銑削後期切屑仍有金屬光澤，表示刀片保持銳利，I1-200N 切削性脫穎而出，綜合以上特性顯示多層膜在刀具保護上更有商用潛力與競爭力。

High-entropy multilayer thin films composed of AlCrNbSiTi and (AlCrNbSiTi)50N50 was sputter-deposited on tungsten carbide. We controlled the film thickness at 1 μm, and then probe into how the number of layers affected the properties of multilayer coatings. For comparison, multilayer, TiN and TiAlN films were annealed at 900oC in air for 2 hours to investigate their oxidation properties. Furthermore, after the milling test of 304 stainless steel, the tungsten carbide insert with optimal multilayer, TiN and TiAlN films were studied to estimate their cutting performance.
The results reveal that the 200-layer films deposited at substrate bias -100 V with period (Ʌ) in 11.2 nm possesses the optimal properties. The hardness of 31.2 GPa and Young’s modulus of 487 GPa illustrate the occurance of the supermodulus phenomenon. From the stair-like cross- section configuration, we can know that the toughness becomes better than single layer coatings. In adhesion test, 200-layer film’s adhesion is classified to the best level, HF1. Besides, the 200-layer coating also has remarkable oxidation resistance and thermal stability. The thickness of oxidation layer is 134 nm measured by transmission electron microscopy, and there is no severe interdiffusion appears at the interface within the films. Possessing the outstanding toughness, adhesion, oxidation resistance, thermal stability and suitable hardness, the tungsten carbide insert with the 200-layer coating performs better than that with TiN, TiAlN coatings in milling test. Above results demonstrate the multilayer coatings have huge potential for the application in the cutting industry.

摘 要 i
Abstract iii
致 謝 v
目 錄 viii
圖目錄 xii
表目錄 xxiii
壹、前 言 1
貳、文獻回顧 4
2.1 薄膜鍍製技術 4
2.1.1 物理氣相沉積 (PVD) 4
2.1.2 濺鍍技術 8
2.1.3 磁控介紹及優點 10
2.1.4 沉積與附著機制 12
2.1.5 微結構 14
2.2 薄膜種類與發展 21
2.2.1 薄膜發展概況 21
2.2.2 薄膜分類與介紹 23
2.2.3.1 本質薄膜 25
2.2.3.2 外延薄膜 26
2.2.3 多層膜強化機制 39
2.2.3.1 Non-ideal composition modulations + dislocation glide within layers 42
2.2.3.2 Hall-Petch strengthening 48
2.3 高熵系統 50
2.3.1 高熵之濫觴 50
2.3.2 高熵合金定義 52
2.3.3 高熵合金特色 55
2.3.4 高熵氮化膜沿革 63
2.4 本論文研究目的 65
參、實驗流程 67
3.1 靶材製作 68
3.2 基板準備 70
3.2.1 基板種類 70
3.2.2 基板前處理 71
3.3 薄膜鍍製 73
3.4 薄膜基本性質分析 77
3.4.1 成分 77
3.4.2 晶格結構 79
3.4.3 薄膜形貌與微結構 79
3.5 薄膜機械性質分析 80
3.5.1 硬度與楊氏係數 80
3.5.2 附著性 82
3.5.3 切削性 84
3.6 薄膜熱性質分析 86
3.6.1 抗氧化性 86
3.6.2 熱穩定性 87
肆、結果與討論 88
4.1 試片命名方法 88
4.2 薄膜層數對未施加偏壓鍍製之多層膜的影響 (W0 系列薄膜) 89
4.2.1 成分確認 89
4.2.2 結構分析 91
4.2.3 表面與橫截面形貌 93
4.2.4 機械性質 97
4.3 薄膜層數對施加 -100 V 偏壓鍍製之多層膜的影響 (W1 系列薄膜) 99
4.3.1 成分分析 99
4.3.2 結構分析 100
4.3.3 表面與橫截面形貌 103
4.3.4 機械性質 107
4.4 W1 系列薄膜與商用 TiN、TiAlN 性質比較 112
4.4.1 附著性測試 114
4.4.2 氧化測試 116
4.4.2.1 氧化層厚度 116
4.4.2.2 TEM 分析 120
4.4.3 切削測試 126
伍、結 論 139
陸、本實驗貢獻 146
柒、未來研究方向 147
參考文獻 148

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