以TiN為主的鈦基氮化物硬膜在工業上的應用已有多時，也由於物理蒸氣沉積俱有操作方便，成本較低的優點，已廣泛地使用在鍍覆各種硬膜。本文即以直流電源電漿反應性濺鍍法將數種鈦基氮化物硬膜鍍覆於不?袗?及工具鋼上，在製程因素控制中，維持110瓦或220瓦的輸入電源，0.8 Pa的工作(真空)壓力，9.3的 Ar/N2 比，攝氏300度的基板溫度，零偏壓輸入以及40分鐘的濺鍍時間，而變化靶材組成，由純Ti靶，Ti-6Al靶，熱壓式Ti-6Al-4V靶以及商用鈦合金Ti-6Al-4V靶作為濺射不同組成的三元或四元性氮化物硬膜。
硬膜機械性質的好壞實繫於附著性的良窳，而常見評估附著性方法有壓印法，刮膜法及衝擊法，由於壓印法操作簡便，設備便宜，極適於硬膜於工具鋼上附著性的量度。本文也先就壓印時作彈性分析，發現在硬膜與期材介面上的剪應力，軸向應力及週向應力與基材的波桑比或降伏強度有密切關係，硬膜鍍在波桑比較大的基材如不?袗?時會在介面引起較大的介面應力及應力集中，所產生的壓印特徵是只在壓印痕?堶惘釵U種裂痕及裂口，而硬膜鍍在波桑比較小的高速鋼上的壓印裂紋則幾乎發現在壓印周圍，良好附著性的硬膜裂紋短少，不良附著性的硬膜也只在壓印週圍產生裂痕及裂口。此外，使用不同荷重的壓印所產生的裂痕程度亦可間接作為量測附著性的方法。
在TiN的硬膜中加了少許的Al(6 wt﹪)或V(4wt﹪)而產生Ti6AlN膜及Ti6Al4VN膜，發現Al使原來晶格常數減少而V會使之回升。兩者的中間層為 –Ti相(固溶入Al及V)而多為柱狀結構，而外層的氮化物，(200)及(100)方向仍然是主要的微結構。當TiAlN中今Fe含量高時，Fe3N-Fe2N(ε)相易優先方向生成。在TiAlVN/HSS中，中間層與基材存在有 的金相關係。
加了少許的Al或V後的TiAlN或TiAlVN在工具鋼上似乎有明顯的耐氧化性質，在本研究中尤其是熱壓靶材所產生的TiAlVN膜於高速鋼上最俱抗氧化傾向，也估算出在攝氏620度-800度富氧環境下氧化的活化能近似於Ti 0.5Al 0.5N於高速鋼的值，亦即抗氧化性質近似，主因是Al高擴散係數所俱有的對氧鈍化的效應以及V所造成的優質硬膜。此外TiAlN及TiAlVN膜在攝氏800度的氧化結構也迴異於TiN者，前兩者不易發現TiN的剝落現象，氧化生成物TiN以Fe2O3為主而前兩者則含多量的Fe2TiO5。

Titanium-based nitride films are deposited on steels by magnetron reactive sputtering for cutting, forming and decorative applications. The nitride films about 2 m thick with interlayer for better adhesion are grown at a working pressure of 0.8 Pa, discharge power of 220 watt, Ar/N2 gas ratio of 0.93, substrate temperature of 300 ℃ and deposition time of 40 minutes. Four different targets (Ti, Ti-6Al, hot-pressed Ti-6Al-4V, commercial Ti-6Al-4V, where Al and V are in wt.%) and two different steels ( stainless steel (SS) and high speed steel (HSS)) as substrate materials are tested.
The indentation technique is used to evaluate the adhesion properties of the nitride films to the substrate and elasticity analysis of indentation to analyze the distribution of the stresses at the interface. The differences in indentation properties
between nitride/ SS and nitride/ HSS are examined and correlated with the elastic/plastic analysis. It appears the cracks and spallings observed inside the indentation cavity in nitride/SS system are due to the higher poisson’s ratio of stainless steel but those around the indentation cavity observed in nitride/HSS system are due to the edge (binding) effect. Continuous load –penetration depth curve of indentation test shows that TiAlVN/HSS is more fracture–resistant than the pure TiN/HSS.
The addition of aluminium into TiN film decreases the lattice constant while further addition of vanadium into TiAlN films causes the lattice constant to increase. This is discussed in terms of bonding characteristics and atomic size of the elements. SEM analysis shows that columnar structure of TiN films is coarser than that of TiAlN and TiAlVN. TEM studies of microstructure and AFM studies of surface roughness show that the TiAlVN film formed by hot–pressed Ti-6Al-4V on HSS has the densest fibrous structure and smoothest surface, and therefore the best mechanical properties such as hardness and indentation fracture resistance.
(111) and (200) orientations of TiN, TiAlN, and TiAlVN are observed by XRD analysis. The ) phase is found due to small amount of Fe in the films. The oxynitride phase in the nitride films as indicated by the binding energy shifts of the elements may be due to the trace oxygen during deposition. The interlayers of TiAlN/HSS and TiAlVN/HSS have the preferred orientations of and . The texture (columnar) structure of (111) and (200) orientations are observed in TiAlN and TiAlVN films. An orientation relationship of is found between interlayer and tempered martensite in TiAlVN/HSS.
Oxidation test was carried out in oxygen atmosphere at 620-800℃for 3 hours. The TiAlVN film by hot-pressed Ti-6Al-4V on HSS follows the parabolic growth law. It also has the slowest oxidation rate while the TiN/ HSS the fastest one. The activation energy of oxidation of this system is about 184.5 kJ/mole.
The oxidation of TiN/ HSS reveals larger area of spallings, while TiAlN/HSS and TiAlVN/ HSS generally show uniform oxidation with small areas of non-uniform growth. There is a dramatic effect of aluminium in facilitating the uniform oxidation for TiAlN and TiAlVN on HSS. The oxidation products of TiAlN/HSS and TiAlVN/ HSS are oxynitride, amorphous Al2O3, Fe2TiO5 and small amount of TiO2 and Fe2O3.

1. Introduction
2. Literature survey
3. Experimental
4. Result
5. Discuss
6. Conclusions
7. Reference
8. Appendix

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