PECVD制备DLC复合薄膜性能及模具应用
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摘要
目的比较分析CrN过渡层与不同膜厚对DLC薄膜性能的影响,以及涂层模具的成型特性。方法采用PECVD方法在718合金试样及模具表面沉积Cr N/DLC复合膜,预设Cr N过渡层厚度为0.2μm,DLC膜层厚度为0.5～1.2μm。采用无损设备对不同沉积时间(10、15、20、25、30、35 min)的薄膜厚度进行表征,并使用扫描电子显微镜(SEM)观察薄膜表面及截面结构特征。采用拉曼光谱(Raman)分析不同厚度DLC膜的峰位信息以及sp3-C/sp2-C的比例关系,用纳米压痕仪表征膜层硬度,用硬度计分析膜/基结合力,用轮廓仪表征薄膜表面特征,并探讨膜厚对薄膜性能的影响机制。结果薄膜的厚度值在预设范围以内,该方法制备的薄膜结构致密,表面光滑,无分层、凹坑、液滴粘附等缺陷。随涂层厚度的增加,薄膜中sp3-C/sp2-C的比例呈先减小后增大的趋势,G峰也先向D峰靠近,而后远离。薄膜硬度同样随膜层厚度的增加呈先增加后减小的趋势,1.06μm厚的Cr N/DLC膜的硬度最高(3600HV)。薄膜的结合力等级最高可以达到工业级的HF2。表面轮廓无较大波动,表面粗糙度Ra最低可达0.011μm。1.06μm CrN/DLC涂层模具的成型寿命是未涂层模具的3倍以上。结论对橡胶模具而言,适当厚度的DLC微/纳涂层处理可以起到一定的减磨、抗腐蚀效果,降低模具本体表面润湿性,保证橡胶件成型质量。
The work aims to compare and analyze the effects of CrN transition layer and different film thickness on the properties of DLC films and the molding characteristics of the coating mold. The CrN/DLC composite films were deposited on the surface of 718 alloy sample and mold by PECVD method. The thickness of the CrN transition layer and DLC film was preset as 0.2 μm and 0.5～1.2 μm respectively. The thickness of films for different deposition time(10 min, 15 min, 20 min, 25 min, 30 min and 35 min) was characterized by non-destructive equipment, and the surface and cross-sectional structure of the films were observed by scanning electron microscopy(SEM). Raman spectroscopy was used to analyze the peak position information and sp3-C/sp2-C ratio of DLC films with different thickness. The nano-indentator was used to characterize the film hardness, the hardness tester was adopted to analyze the adhesion strength of film and substrate and the profilometer was applied to characterize surface features. Moreover, all the mechanisms leading to the above effects were discussed. The thickness of all the films was within the preset range. The film structure fabricated by this method was compact, smooth, and free from defects such as delamination, pits, droplet adhesion, etc. The ratio of sp3-C/sp2-C in the film decreased and then increased with the increase of coating thickness, and the G peak approached D peak first and then went away. The hardness of film also increased with the increase of film thickness, and then decreased. 1.6 μm thick film had the highest hardness(HV3600). The highest adhesion strength of the film could reach HF2 of the industrial grade. The surface profile was free from greater range of fluctuations, and the minimum surface roughness Ra could reach 0.011 μm. The service life of the coating mold was increased by at least 1.5 times. For rubber mold, suitable thickness of DLC micro-nano coating can reduce wear and corrosion, lower the surface wettability of the mold body, and ensure the forming quality of rubber parts.
The work aims to compare and analyze the effects of CrN transition layer and different film thickness on the properties of DLC films and the molding characteristics of the coating mold. The CrN/DLC composite films were deposited on the surface of 718 alloy sample and mold by PECVD method. The thickness of the CrN transition layer and DLC film was preset as 0.2 μm and 0.5～1.2 μm respectively. The thickness of films for different deposition time(10 min, 15 min, 20 min, 25 min, 30 min and 35 min) was characterized by non-destructive equipment, and the surface and cross-sectional structure of the films were observed by scanning electron microscopy(SEM). Raman spectroscopy was used to analyze the peak position information and sp3-C/sp2-C ratio of DLC films with different thickness. The nano-indentator was used to characterize the film hardness, the hardness tester was adopted to analyze the adhesion strength of film and substrate and the profilometer was applied to characterize surface features. Moreover, all the mechanisms leading to the above effects were discussed. The thickness of all the films was within the preset range. The film structure fabricated by this method was compact, smooth, and free from defects such as delamination, pits, droplet adhesion, etc. The ratio of sp3-C/sp2-C in the film decreased and then increased with the increase of coating thickness, and the G peak approached D peak first and then went away. The hardness of film also increased with the increase of film thickness, and then decreased. 1.6 μm thick film had the highest hardness(HV3600). The highest adhesion strength of the film could reach HF2 of the industrial grade. The surface profile was free from greater range of fluctuations, and the minimum surface roughness Ra could reach 0.011 μm. The service life of the coating mold was increased by at least 1.5 times. For rubber mold, suitable thickness of DLC micro-nano coating can reduce wear and corrosion, lower the surface wettability of the mold body, and ensure the forming quality of rubber parts.
引文
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[2]张而耕,陈强.类金刚石涂层的研究进展及其应用[J].粉末冶金工业,2015,25(5):60-65.ZHANG Er-geng,CHEN Qiang.Research progress and application of diamond-like carbon coating[J].Powder metallurgy industry,2015,25(5):60-65.
[3]张而耕,朱州,张体波.超硬纳微米PVD涂层技术在模具领域的发展[J].表面技术,2014(5):118-123.ZHANG Er-geng,ZHU Zhou,ZHANG Ti-bo.Development of super hard nanomicron PVD coating technology in the field of mold[J].Surface technology,2014(5):118-123.
[4]ZHAO G H,AUNE R E,ESPALLARGAS N.Tribocorrosion studies of metallic biomaterials:The effect of plasma nitriding and DLC surface modifications[J].Journal of the mechanical behavior of biomedical materials,2016,63:100-114.
[5]WANG J,MA J,HUANG W,et al.The investigation of the structures and tribological properties of F-DLC coatings deposited on Ti-6Al-4V alloys[J].Surface and coatings technology,2017,316:22-29.
[6]ERDEMIR A.The role of hydrogen in tribological properties of diamond-like carbon films[J].Surface and coatings technology,2001,146-147:292-297.
[7]DALIBON E L,ESCALADA L,SIMISON S,et al.Mechanical and corrosion behavior of thick and soft DLCcoatings[J].Surface and coatings technology,2017,312:101-109.
[8]MULLER I C,SHARP J,RAINFORTH W M,et al.Tribological response and characterization of Mo-W doped DLC coating[J].Wear,2017,376-377:1622-1629.
[9]BACHMANN S,SCHULZE M,MORASCH J,et al.Aging of oxygen and hydrogen plasma discharge treated a-C:H and Ta-C coatings[J].Applied surface science,2016,371:613-623.
[10]OUCHABANE M,HASSANI S,DUBLANCHETIXIERC,et al.Effect of DLC films thickness on residual stress and mechanical properties[J].Science of advanced materials,2015,7(7):157-162.
[11]安书董,王晓燕,陈仙,等.基底表面纳米织构对非晶四面体碳膜结构和摩擦特性的影响研究[J].物理学报,2015,64(3):440-445.AN Shu-dong,WANG Xiao-yan,CHEN Xian,et al.Effect of ion-beam surface modification technology on the variation of surface texture[J].Acta phys sin,2015,64(3):440-445.
[12]?RFAN U,ASLANTAS K,BEDIR F.The performance of DLC-coated and uncoated ultra-fine carbide tools in micromilling of inconel 718[J].Precision engineering,2015,41:135-144.
[13]RAY S C,PONG W F,PAPAKONSTANTINOU P.Iron,nitrogen and silicon doped diamond like carbon(DLC)thin films:A comparative study[J].Thin solid films,2016,610:42-47.
[14]BOBZIN K,BAGCIVAN N,IMMICH P,et al.Advancement of a nano-laminated TiHfN/CrN PVD tool coating by a nano-structured CrN top layer in interaction with a biodegradable lubricant for green metal forming[J].Surface and coatings technology,2009,203:3184-3188.
[15]SOLIS J,ZHAO H,WANG C,et al.Tribological performance of an H-DLC coating prepared by PECVD[J].Applied surface science,2016,383:222-232.
[16]TSOTSOS C,BAKER M A,POLYCHRONOPOULOU K,et al.Structure and mechanical properties of low temperature magnetron sputtered nanocrystalline(NC-)Ti(N,C)/amorphous diamond like carbon(a-C:H)coatings[J].Thin solid films,2010,519:24-30.
[17]QU Sheng-guan,SUN Fu-jian,ZHANG Liang,et al.Effects of cutting parameters on dry cutting of aluminum bronze alloy[J].The international journal of advanced manufacturing technology,2014,70(1):669-698.