臺灣博碩士論文加值系統

　　低溫電漿技術被覆陶瓷硬質鍍層(Ceramic hard coating)已廣泛應用在工具上以提昇使用壽命。氮化鈦為目前工具被覆最廣泛使用的陶瓷硬質鍍層之一。但在某些高剪力、高衝擊力的磨耗環境下，鍍層往往以非正常的磨耗被消耗掉，最嚴重的情況是剝落(Spallation)型式磨耗，這些剝落的硬質鍍層以研磨方式加速工具的磨耗，此一現象可歸因於硬質鍍層與工具之間的硬度差異過大所致。此外，磨潤過程中鍍層與基材間之附著性亦是重要的考量因素，由於電漿製程之基材溫度較低，使得鍍層之附著性差。因此，本研究以無電鍍Ni-P-SiC複合鍍層作為SKD61模具鋼與氮化鈦硬質鍍層之中間介層，希望所用SiC硬質粒子的添加可強化無電鍍Ni-P鍍層，提高工具之負荷承載的能力，延長其使用壽命。主要研究內容為無電鍍Ni-P-SiC複合鍍層，及其對氮化鈦鍍層的表面視硬度、附著性及耐磨耗性的影響。

　　研究顯示藉由複合無電鍍法可成功合成Ni-P-SiC複合鍍層，鍍層之SiC含量隨鍍浴中SiC添加量增加而增加，但鍍層成長速率則隨之下降。初鍍膜及400℃以下熱處理之Ni-P-SiC複合鍍層的結構與Ni-P鍍層相同，不因SiC添加而產生結構上的變化。但經450℃以上熱處理時，SiC熱分解，並與Ni反應生成g-Ni5Si2、b1-Ni3Si和石墨相。複合鍍層在400℃時達最大硬化效果與最低磨耗係數，進一步提高熱處理溫度，則因g-Ni5Si2、b1-Ni3Si和石墨相生成，複合鍍層之硬度下降，耐磨耗性亦隨之降低。

　　TiN/Ni-P-SiC複合鍍層的表面視硬度隨Ni-P-SiC中介層中SiC含量增加而增加。硬度值的提升是由於部分TiN沉積在SiC硬粒子上以及因SiC微粒的添加進一步強化無電鍍Ni-P中介層，提高其負荷承載能力來支撐TiN鍍層。與單層的氮化鈦鍍層及TiN/Ni-P複合鍍層比較，可發現TiN/Ni-P-SiC複合鍍層，無論是磨耗的寬度及深度都大幅下降。耐磨耗性的提升可歸因於SiC粒子加入Ni-P中介層，使得TiN鍍層的表面視硬度與附著強度提高，因而提升整體的耐磨耗性。

　　The use of hard ceramic coatings in industry is now well established, particularly in applications where wear resistance is an important consideration. TiN deposited either by CVD or low-temperature-plasma processes (PECVD or PVD) is commonly used as coating material. But in some cases, cracking and spalling of the TiN layer may accelerate the wear rate of tools under severe conditions. This could be due to an abrupt hardness difference existing between the TiN coating and the substrate. Besides, the adhesion of coating-substrate system is another important factor in tribological processes. In PECVD or PVD process, which works at lower substrate temperatures, little interaction takes place between the coating and the substrate, resulting in a poor adhesion. Therefore, researchers proposed the hybrid processes to overcome this problem. In other words, the hardness and/or adhesion of coating-substrate system can be enhanced by introducing an appropriate interlayer between them.

　　In this study, an attempt was made to further improve the mechanical properties of TiN/Ni-P hybrid coating by adding b-SiC particles into the Ni-P interlayer. A hybrid process that combines composite electroless plating and plasma-enhanced chemical vapor deposition was proposed to improve the mechanical properties of TiN coated tool steel. The hardness, adhesion, and sliding wear resistance of hybrid-coated SKD61 tools were investigated.

　　Experimental results show that SiC particles were successfully incorporated in the Ni-P alloy matrix by electroless composite plating method. The content of SiC in the composite coating increases with increasing SiC concentration in the plating bath, but decreases growth rate of the Ni-P-SiC composite coatings. The SiC particle addition did not change the structure of the Ni-P alloy matrix significantly when the annealing temperature was below 400oC. However, by raising the annealing temperature up to 450oC, the SiC particles decomposed and reacted with nickel to form g-Ni5Si2, b1-Ni3Si and graphite. The hardness and wear resistance of the composite coatings can be increased to a maximum at a temperature of 400oC, over which the coating experiences the formation of g-Ni5Si2, b1-Ni3Si and graphite and the mechanical strength is decreased.

　　The apparent hardness of the TiN/Ni-P-SiC hybrid coatings increases with increasing content of SiC particles in electroless Ni-P interlayer and affects the TiN hardness value. This could be due to an effect of SiC particles added on the coating growth of TiN and a high load carrying capability of Ni-P-SiC interlayer. In comparison with single TiN layer and TiN/Ni-P hybrid coating, a reduction in cracking and spalling for the TiN/Ni-P-SiC layer was observed during wear tests. Wear resistance is significantly improved due to the incorporation of SiC particles into electroless Ni-P interlayer, which increases hardness and adhesion of the coated TiN layer.

中文摘要 I
英文摘要 III
總目錄 V
表目錄 VIII
圖目錄 IX
英漢名詞與符號對照表 XIII

第一章 緒論 1
第二章 理論基礎 5
　2-1 無電鍍鎳原理 5
　　2-1-1 無電鍍鎳原理 5
　　2-1-2 無電鍍鎳鍍層結構與特性 7
　2-2 無電鍍複合鍍層 10
　　2-2-1 複合鍍層簡介 10
　　2-2-2 複合鍍層之沉積機構 12
　2-3 電漿化學氣相沉積 14
　　2-3-1 低壓電漿反應 14
　　2-3-2 電漿化學氣相沉積熱力學分析 17
　　2-3-3 電漿化學氣相沉積動力學分析 17
　2-4 附著性測試 22
　2-5 磨耗行為 25

第三章 實驗方法與步驟 28
　3-1 實驗流程 28
　3-2 系統設計與安裝 29
　　3-2-1 複合無電鍍系統 29
　　3-2-2 電漿化學氣相沉積系統 31
　3-3 材料的選擇 34
　3-4 實驗參數與步驟 37
　　3-4-1 無電鍍Ni-P-SiC複合析鍍 37
　　3-4-2 氮化鈦之被覆條件 41
　3-5 鍍層性質分析 43
　　3-5-1 鍍層本質分析 43
　　3-5-2 鍍層機械性質測試 45

第四章 無電鍍Ni-P-SiC複合鍍層 49
　4-1 前人研究與實驗動機 49
　4-2 鍍層之成長特性 50
　　4-2-1 鍍層之成分分析 50
　　4-2-2 鍍層之成長速率 50
　4-3 鍍層之表面型態觀察 54
　4-4 添加SiC粒子對無電鍍Ni-P鍍層結構之影響 57
　　4-4-1 X光繞射分析 57
　　4-4-2 穿透式電子顯微鏡分析 61
　4-5 鍍層之表面視硬度 72
　　4-5-1 無電鍍Ni-P鍍層之表面視硬度 72
　　4-5-2 添加SiC粒子對無電鍍Ni-P鍍層表面視硬度之影響 75
　　4-5-3 熱處理溫度對複合鍍層表面視硬度之影響 75
　4-6 添加SiC粒子對無電鍍Ni-P鍍層附著性之影響 78
　　4-6-1 鍍層壓痕型態 78
　　4-6-2 鍍層之附著性 80
　4-7 無電鍍Ni-P-SiC複合鍍層之磨耗行為 84
　4-8 結論 89

第五章 Ni-P-SiC中介層對TiN陶瓷面層磨潤性質之研究 91
　5-1 前人研究與實驗動機 91
　5-2 氮化鈦鍍層之微觀型態 96
　5-3 複合被覆鍍層之表面視硬度 101
　5-4 氮化鈦鍍層之附著性 104
　5-5 複合被覆鍍層之磨耗行為 109
　5-6 結論 119

第六章 總結論 120

參考文獻 123
致謝 131
自述 132

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