表面工程技術是藉由表面改質或是表面鍍膜來保護工件、延長使用壽命、降低生產成本以及擴展應用領域。而硬質鍍膜由於具有高強度、抗氧化、抗腐蝕、耐磨耗等機械特性，可廣泛使用在各種工業領域，例如切削刀具保護層以及包含手機、筆記型電腦等3C產品的裝飾鍍層等。本研究先試以新穎之鈦鋁鉻矽釩高熵合金作為磁控濺鍍靶材，藉由反應性氮氣流量的調變可製備出各式不同氮含量的氮化物。在微結構鑑定中可發現，氮化鈦鋁鉻矽釩展現出其因多元而特有的奈米晶結構，達計量比的多元氮化物其硬度在製程中施加偏壓後可達到36 GPa，大幅優於傳統的二元或三元氮化物。在耐蝕性的測試中發現，多元的鈦鋁鉻矽釩雖然硬度較低，但其非晶態結構在作為硬質氮化物的中間層時，能有效阻止電解液的滲透，並使多元氮化物成長得更為緻密，有效提升薄膜的抗腐蝕特性。然而藉由電子顯微鏡的相鑑定後發現，在超過700 oC的大氣環境下，二氧化鈦以及四氧化鉻釩的生成將破壞此多元氮化膜原本緻密的結構。為了同時使多元薄膜兼具良好的耐蝕性以及高溫抗氧化性，在後期研究中嘗試以去除鈦、釩的鉻鋁合金作為靶材，與矽靶進行氮化鉻鋁之共鍍，由微結構分析中發現矽添加有促進薄膜非晶化的效果，藉由非晶態氮化矽的生成可有效地將薄膜的柱狀晶結構轉變為緊密的等軸晶結構，具備奈米複合材結構的氮化鉻鋁除了具有超過30 GPa的高硬度外，其細緻的微結構亦使得薄膜具有優良的抗腐蝕特性。

Surface modification engineering is the technology to deposit a foreign material onto the surface of interest to improve specific desired properties. This study aimed to develop a new multi-component material as a protective coating, which would enhance the surface strength, thermal stability, and corrosion resistance of the tool steels. The multi-component (TiAlCrSiV)xNy coatings were fabricated by utilizing a high entropy alloy (HEA) target in RF magnetron sputtering. Through hardness measurements, wear tests, heat treatments, and corrosion tests, effect of each additional element in harsh environments was evaluated. The multi-component (TiAlCrSiV)xNy nitrides (denoted as MCN in the following text) exhibited a f.c.c. crystallined structure and an enhanced hardness as high as 36.4 GPa. According to the XRD patterns and TEM analyses, the improved mechanical properties were attributed to their nano-crystalline structures. After a heat treatment at 600 oC in air, a mixed amorphous oxide layer formed on the surface of MCN coating and protected the coating from further oxygen attack. Subsequently, the formations of CrVO4 and TiO2 were verified after annealing the coating at 700 oC in air. The outward diffusion of Ti, revealed by EDS quantitative data, implied that these crystalline oxides no longer acted as a protection and serious oxidation occurred from this temperature. Due to the absence of self-lubricating V2O5 oxide, the reduced friction coefficient was only found in the as-deposited MCN coatings. Although addition of Ti and V was disfavored in consideration of oxidation, the multi-component TiAlCrSiV coating (denoted as MC in the following text) revealed its amorphous nature as well as good corrosion resistance against NaCl solution. Being a metallic interlayer between coating and steel substrates, it also greatly improved the polarization resistance of the steel/MC/MCN sample. Hence, the coated tools could reveal both enhanced surface hardness and improved corrosion resistance.
Concerning about both oxidation and corrosion resistance, Ti and V were removed in the parallel study, and the amorphization was achieved by adjusting the Si content of the modified coating. The nanocomposite structure of the modified CrAlSiN coating was investigated by TEM techniques, and the grain refinement by adding Si was verified. It was found that the columnar structure of CrAlN coating could be altered to a compact one after Si addition, and the polarization resistance of the coated sample was thus improved. Therefore, the CrAlSiN coating with high hardness, good thermal stability and corrosion resistance was suggested as a potential candidate coating for tool steels.

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