梯度成分结构TiAlSiYN涂层的制备及其抗氧化性能研究
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摘要
目的采用阴极电弧镀叠加磁控溅射的复合PVD涂层技术,实现梯度成分结构Ti AlSiYN多元涂层的制备。方法在涂层沉积过程中,通过切换不同成分的电弧靶,获得成分梯度变化的Ti AlSiYN涂层。利用扫描电子显微镜及其附带能谱仪、X射线衍射仪分析涂层氧化前后的截面组织形貌、成分和物相结构。结果在阴极电弧沉积过程中,通过磁控溅射方式植入微量Y元素会干扰涂层的生长,降低涂层的生长速率。Y元素在涂层中具有细化柱状组织的作用,并使涂层的开始氧化温度和氧化速率降低。相比于均一成分结构的Ti AlSiN涂层,均一成分结构的Ti AlSiYN涂层在800℃时表层未发生氧化。在900℃保温1 h后,Ti AlSiYN涂层的高氧含量氮氧化物层厚度小于Ti AlSiN涂层。梯度成分结构使Ti AlSiYN涂层的抗氧化性能明显降低,在900℃保温1 h后,梯度成分结构的Ti AlSiYN涂层组织完全被氧化,氧化组织以金红石结构的Ti O2为主,还有少量锐钛矿结构的Ti O2、Si O2和Al2O3。结论微量稀土Y元素具有改善涂层抗氧化性的作用,而梯度成分结构不利于涂层的抗氧化性。
The work aims to deposit the TiAlSiYN multi-component coatings with gradient composition structure by com-posite PVD coating technique combining cathodic arc plating and magnetron sputtering. In the deposition process, the TiAl-SiYN coating with changing gradient compositional structure was obtained by switching the arc targets. Scanning electron mi-croscopy and its accompanying spectrometer and X-ray diffractometer were used to analyze the cross-sectional microstructure,composition and phase structure of the coating before and after oxidation. The implantation of trace amounts of yttrium by mag-netron sputtering in the process of cathodic arc deposition interfered with the growth of the coating and reduced the growth raterate of the coating. Y element had the function of refining the columnar structure in the coating, and lowering the initial oxida-tion temperature and oxidation rate of the coating. Compared with the TiAlSiN coating with homogeneous composition, the sur-face of the TiAlSiYN coating with homogeneous composition was not oxidized at 800 ℃. The thickness of the high-oxygenoxynitride layer was less than that of the TiAlSiN coating after being kept at 900 ℃ for 1 h. The graded-composition structuresignificantly reduced the oxidation resistance of the TiAlSiYN coating. After being kept at 900 ℃ for 1 h, the TiAlSiYN coat-ings with graded-composition structure were completely oxidized. The oxidized structure mainly included rutile-TiO2, and asmall amount of anatase-TiO2, SiO2 and Al2 O3. Therefore, the rare earth element Y has an effect of improving the oxidation re-sistance of the coating while the gradient composition structure is detrimental to the oxidation resistance of the coating.
The work aims to deposit the TiAlSiYN multi-component coatings with gradient composition structure by com-posite PVD coating technique combining cathodic arc plating and magnetron sputtering. In the deposition process, the TiAl-SiYN coating with changing gradient compositional structure was obtained by switching the arc targets. Scanning electron mi-croscopy and its accompanying spectrometer and X-ray diffractometer were used to analyze the cross-sectional microstructure,composition and phase structure of the coating before and after oxidation. The implantation of trace amounts of yttrium by mag-netron sputtering in the process of cathodic arc deposition interfered with the growth of the coating and reduced the growth raterate of the coating. Y element had the function of refining the columnar structure in the coating, and lowering the initial oxida-tion temperature and oxidation rate of the coating. Compared with the TiAlSiN coating with homogeneous composition, the sur-face of the TiAlSiYN coating with homogeneous composition was not oxidized at 800 ℃. The thickness of the high-oxygenoxynitride layer was less than that of the TiAlSiN coating after being kept at 900 ℃ for 1 h. The graded-composition structuresignificantly reduced the oxidation resistance of the TiAlSiYN coating. After being kept at 900 ℃ for 1 h, the TiAlSiYN coat-ings with graded-composition structure were completely oxidized. The oxidized structure mainly included rutile-TiO2, and asmall amount of anatase-TiO2, SiO2 and Al2 O3. Therefore, the rare earth element Y has an effect of improving the oxidation re-sistance of the coating while the gradient composition structure is detrimental to the oxidation resistance of the coating.
引文
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[3]KANG S U,LIU D M,SHAO T M.Microstructure and mechanical properties of TiAlSiN nano-composite coatings deposited by ion beam assisted deposition[J].Science China technological sciences,2015,58(10):1682-1688.
[4]ZHANG S,CAI F,LI M.The nanostructured phase transition and thermal stability of superhard f-TiN/h-AlSiNfilms[J].Surface&coatings technology,2012,206(17):3572-3579.
[5]ZHU L H,SONG C,WANGYANG N I,et al.Effect of10%Si addition on cathodic arc evaporated TiAlSiN coatings[J].Transactions of nonferrous metals society of China,2016,26(6):1638-1646.
[6]SUI X,LI G,QIN X,et al.Relationship of microstructure,mechanical properties and titanium cutting performance of TiAlN/TiAlSiN composite coated tool[J].Ceramics international,2016,42(6):7524-7532.
[7]DAS P,ANWAR S,BAJPAI S,et al.Structural and mechanical evolution of TiAlSiN nanocomposite coating under influence of Si3N4 power[J].Surface&coatings technology,2016,307:676-682.
[8]CHEN J K,CHANG C L,SHIEH Y N,et al.Structures and properties of(TiAlSi)N films[J].Procedia engineering,2012,36(6):335-340.
[9]ZHU L,HU M,NI W,et al.High temperature oxidation behavior of Ti0.5Al0.5N coating and Ti0.5Al0.4Si0.1N coating[J].Vacuum,2012,86(12):1795-1799.
[10]CHANG Y Y,YANG S M.High temperature oxidation behavior of multicomponent Ti AlSiN coatings[J].Thin solid films,2010,518:34-37.
[11]鲜广,赵海波,范洪远,等.磁控溅射法制备Zr Al YN涂层的结构和性能[J].中国表面工程,2013,26(5):12-17.XIAN Guang,ZHAO Hai-bo,FAN Hong-yuan,et al.Structure and properties of ZrAlYN coating deposited by magnetron sputtering[J].China surface engineering,2013,26(5):12-17.
[12]MA Q,LI L,XU Y,et al.Effect of Ti content on the microstructure and mechanical properties of TiAlSiN nanocomposite coatings[J].International journal of refractory metals&hard materials,2016,59:114-120.
[13]CHEN L,DU Y,WANG A J,et al.Effect of Al content on microstructure and mechanical properties of Ti-Al-Si-Nnanocomposite coatings[J].International journal of refractory metals&hard materials,2009,27(4):718-721.
[14]ZHOU M,MAKINO Y,NOSE M,et al.Phase transition and properties of Ti-Al-N thin films prepared by r.f.-plasma assisted magnetron sputtering[J].Thin solid films,1999,339(1-2):203-208.
[15]DU M,HAO L,LIU X,et al.Microstructure and thermal stability of Ti1-xAlxN coatings deposited by reactive magnetron co-sputtering[J].Physics procedia,2011,18(1):222-226.
[16]KIMURA A,MURAKAMI T,YAMADA K,et al.Hot-pressed Ti-Al targets for synthesizing Ti1-xAlxN films by the arc ion plating method[J].Thin solid films,2001,382(1):101-105.
[17]MAN B Y,GUZMAN L,MIOTELLO A,et al.Microstructure,oxidation and H2-permeation resistance of TiAlN films deposited by DC magnetron sputtering technique[J].Surface&coatings technology,2004,180(3):9-14.
[18]XIAN Guang,ZHAO Hai-bo,FAN Hong-yuan,et al.The structure and properties of ZrAl(Y)N coatings deposited at various N2/Ar flow ratios[J].International journal of refractory metals&hard materials,2014,44(3):60-67.
[19]XU Y X,RIEDL H,HOLEC D,et al.Thermal stability and oxidation resistance of sputtered Ti-Al-Cr-N hard coatings[J].Surface&coatings technology,2017,324:48-56.
[20]HE N,LI H,LI J,et al.High temperature tribological properties of TiAlSiN coatings produced by hybrid PVDtechnology[J].Tribology international,2016,98:133-143.
[21]PINT B A.Experimental observations in support of the dynamic-segregation theory to explain the reactive-element effect[J].Oxidation of metals,1996,45(1-2):1-37.