不锈钢根管锉镀覆TiN、ZrN膜的沉积工艺与性能研究
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摘要
目的通过在不锈钢根管锉表面镀覆Ti N、Zr N薄膜,以提高其切削性能。方法采用磁控溅射技术,调整沉积时间、基片偏压、占空比等工艺参数在不锈钢根管锉上分别沉积Ti N、Zr N薄膜。对Ti N、Zr N膜层进行SEM断面分析、XRD相组成分析、表面硬度测试、膜层附着力测试,考查了Ti N、Zr N薄膜的厚度、相组成、硬度以及附着力。通过对镀膜后的根管锉进行电化学腐蚀试验、模拟临床切削试验,分析了镀膜后根管锉的耐蚀性和切削性能。结果随着工艺参数的变化,Ti N、ZrN薄膜的厚度、相结构以及硬度均显示了规律性的变化。镀覆Ti N、Zr N薄膜的不锈钢根管锉的自腐蚀电流密度相对于未镀膜的根管锉均明显降低。确定了Ti N膜层和Zr N膜层的优化沉积工艺分别为沉积时间1 h、负偏压100 V、占空比60%和沉积时间1h、负偏压150V、占空比60%。优化工艺下镀膜的不锈钢根管锉的切削数量和切削效率显著提高。结论和未镀膜不锈钢根管锉相比,镀覆Ti N、ZrN薄膜的不锈钢根管锉的表面硬度、耐蚀性能均有显著提高。最优工艺下制备的镀覆Ti N、Zr N薄膜的不锈钢根管锉兼具切削数量、切削效率以及切削稳定性等方面的综合优势,和未镀膜不锈钢根管锉相比,切削效率提高60%～75%,切削树脂模拟根管数量达到1.7～2倍,实现了切削性能的显著提升。
The work aims to improve cutting performance of stainless steel root files by coating TiN and ZrN films on the surface. TiN and ZrN thin films were deposited on stainless steel root canal files by magnetron sputtering with adjusting deposition time, substrate bias and duty cycle. The thickness, phase composition, hardness and adhesion of the TiN and ZrN films were examined by SEM, XRD and surface hardness and adhesion tests. The corrosion resistance and the cutting performance of the coated root canal files were analyzed by the electrochemical corrosion test and the simulated clinical cutting test. The thickness,phase structure and hardness of the TiN and ZrN films changed with the deposition process parameters. The corrosion current density of stainless steel root canal files coated with TiN and ZrN films decreased significantly compared with that of the uncoated ones. The optimized deposition processes of TiN and ZrN films were determined to be: deposition time of 1 h, negative bias of 100 V and duty cycle of 60% and 1 h, negative bias of 150 V and duty cycle of 60% respectively. The cutting quantity and efficiency of stainless steel root canal files coated with the optimized process were significantly improved. Compared with the uncoated ones, the stainless steel root canal files coated with TiN and ZrN films improve significantly the surface hardness and corrosion resistance. The stainless steel root canal files optimally coated with TiN and ZrN thin films exhibit the multiple advantages of cutting quantity, cutting efficiency and cutting stability. The cutting efficiency is increased by 60%～75%, and the number of the cut resin root canals is 1.7～2 times in comparison with the uncoated stainless steel root canal files. The remarkable improvements in cutting performance are achieved.
The work aims to improve cutting performance of stainless steel root files by coating TiN and ZrN films on the surface. TiN and ZrN thin films were deposited on stainless steel root canal files by magnetron sputtering with adjusting deposition time, substrate bias and duty cycle. The thickness, phase composition, hardness and adhesion of the TiN and ZrN films were examined by SEM, XRD and surface hardness and adhesion tests. The corrosion resistance and the cutting performance of the coated root canal files were analyzed by the electrochemical corrosion test and the simulated clinical cutting test. The thickness,phase structure and hardness of the TiN and ZrN films changed with the deposition process parameters. The corrosion current density of stainless steel root canal files coated with TiN and ZrN films decreased significantly compared with that of the uncoated ones. The optimized deposition processes of TiN and ZrN films were determined to be: deposition time of 1 h, negative bias of 100 V and duty cycle of 60% and 1 h, negative bias of 150 V and duty cycle of 60% respectively. The cutting quantity and efficiency of stainless steel root canal files coated with the optimized process were significantly improved. Compared with the uncoated ones, the stainless steel root canal files coated with TiN and ZrN films improve significantly the surface hardness and corrosion resistance. The stainless steel root canal files optimally coated with TiN and ZrN thin films exhibit the multiple advantages of cutting quantity, cutting efficiency and cutting stability. The cutting efficiency is increased by 60%～75%, and the number of the cut resin root canals is 1.7～2 times in comparison with the uncoated stainless steel root canal files. The remarkable improvements in cutting performance are achieved.
引文
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[14]WANG L,SU J F,NIE X.Corrosion and tribological properties and impact fatigue behaviors of TiN-and DLC-coated stainless steels in a simulated body fluid environment[J].Surface&coatings technology,2010,205(5):1599-1605.
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[19]李洪涛,蒋百灵,杨波,等.电场环境对磁控溅射纯Cr薄膜沉积过程的影响[J].功能材料,2010,41(11):2006-2009.LI Hong-tao,JIANG Bai-ling,YANG Bo,et al.Effect of electric field environment on the process of depositing pure Cr films by magnetron sputtering[J].Journal of functional materials,2010,41(11):2006-2009.
[20]李洪涛,蒋百灵,曹政.占空比对磁控溅射纯Cr镀层微观组织结构的影响[J].真空科学与技术学报,201030(2):133-137.LI Hong-tao,JIANG Bai-ling,CAO Zheng.Influence of duty cycle on microstructures of magnetron sputtered pure Cr coatings[J].Chinese journal of vacuum science and technology,2010,30(2):133-137.
[21]王珍,杨得全.一些金属、半导体和化合物的Ar+溅射产额[J].真空与低温,1990(3):51-56.WANG Zhen,YANG De-quan.Ar+sputtering yields of some metals,semiconductors and compounds[J].Vacuum and cryogenics,1990(3):51-56.
[22]赵升升,周晟昊,余红雅,等.厚度对TiN薄膜力学性能的影响[J].真空科学与技术学报,2016,36(3):291-295.ZHAO Sheng-sheng,ZHOU Sheng-hao,YU Hong-ya,et al.Effect of TiN filmsthickness on mechanical properties of stainless steel[J].Chinese journal of vacuum science and technology,2016,36(3):291-295.
[23]袁琳,高原,张维,等.负偏压对多弧离子镀TiN薄膜的影响[J].表面技术,2012,41(1):20-26.YUAN Lin,GAO Yuan,ZHANG Wei,et al.Effect of negative bias voltage on Ti N coating deposited by MAIP[J].Surface technology,2012,41(1):20-26.
[24]魏永强,张艳霞,文振华,等.脉冲偏压占空比对TiN/TiAlN多层薄膜微观结构和硬度的影响[J].表面技术,2014,43(1):1-6.WEI Yong-qiang,ZHANG Yan-xia,WEN Zhen-hua,et al.Effect of different pulse bias duty cycleon themicrostructure and hardness of TiN/TiAlN multilayer coatings[J].Surface technology,2014,43(1):1-6.
[25]WOKULSKI Z.Mechanical properties of TiN whiskers[J].Physica status solidi,2010,120(1):175-184.
[26]李成明,孙晓军,张增毅,等.ZrN及其多层膜的性质和耐腐蚀性能[J].材料热处理学报,2003,24(4):55-58.LI Cheng-ming,SUN Xiao-jun,ZHANG Zeng-yi,et al.Properties and corrosion resistant of ZrN and ZrN/TiNmultilayer films[J].Transactions of materials and heat treatment,2003,24(4):55-58.
[27]余存烨.锆与钛耐蚀性比较及应用互补性[J].腐蚀与防护,2007,28(5):223-226.YU Cun-ye.Comparison of corrosion resistance of zirconium and titanium and their complementarity in applications[J].Corrosion&protection,2007,28(5):223-226.
[2]TA?DEMIR T,ER K,YILDIRIM T,et al.Efficacy of three rotary Ni Ti instruments in removing gutta-percha from root canals[J].International endodontic journal,2010,41(3):191-196.
[3]BüRKLEIN S,MATHEY D,SCH?FER E.Shaping ability of protaper NEXT and BT-RaCe nickel-titanium instruments in severely curved root canals[J].International endodontic journal,2015,48(8):774-781.
[4]陈菁,夏凌云,陈新梅.根管治疗术中镍钛器械折断因素的研究进展[J].牙体牙髓牙周病学杂志,2008,18(3):177-180.CHEN Jing,XIA Ling-yun,CHEN Xin-mei.Research development of fracture factors of nickel-titanium instruments in root canal therapy[J].Chinese journal of conservative dentistry,2008,18(3):177-180.
[5]MADARATI A A,HUNTER M J,DUMMER P M.Management of intracanal separated instruments[J].J endod,2013,39(5):569-581.
[6]PARASHOS P,MESSER H H.Rotary Ni Ti instrument fracture and its consequences[J].Journal of endodontics,2006,32(11):1031-1043.
[7]MARTíN B,ZELADA G,VARELA P,et al.Factors influencing the fracture of nickel-titanium rotary instruments[J].International endodontic journal,2010,36(4):262-266.
[8]SCH?FER E.Effect of physical vapor deposition on cutting efficiency of nickel-titanium files[J].Journal of endodontics,2002,28(12):800-802.
[9]SCH?FER E.Effect of sterilization on the cutting efficiency of PVD-coated nickel-titanium endodontic instruments[J].International endodontic journal,2010,35(10):867-872.
[10]AUN D P,PEIXOTO I F,HOUMARD M,et al.Enhancement of NiTi superelastic endodontic instruments by TiO2 coating[J].Materials science&engineering C,2016,68:675-680.
[11]逄爱慧,李明,陈美玲,等.Ni Ti根管器械表面耐磨镀层的制备和性能研究[J].临床口腔医学杂志,2013,29(10):582-585.PANG Ai-hui,LI Ming,CHEN Mei-ling,et al.The fabrication process and properties of the wearable coating on the surface of NiTi alloy endodon[J].Journal of clinical stomatology,2013,29(10):582-585.
[12]钱鑫,康国鹏,樊红霞,等.镀膜对镍钛器械抗腐蚀性影响临床研究[J].中国实用口腔科杂志,2016,9(11):672-675.QIAN Xin,KANG Guo-peng,FAN Hong-xia,et al.Study on the corrosion resistance of coated nickel-titanium endodontic instruments[J].Chinese journal of practical stomatology,2016,9(11):672-675.
[13]YAMAUCHI N,OKAMOTO A,TUKAHARA H,et al.Friction and wear of DLC films on 304 austenitic stainless steel in corrosive solutions[J].Surface&coatings technology,2003,174(3):465-469.
[14]WANG L,SU J F,NIE X.Corrosion and tribological properties and impact fatigue behaviors of TiN-and DLC-coated stainless steels in a simulated body fluid environment[J].Surface&coatings technology,2010,205(5):1599-1605.
[15]STAIA M H,PUCHI-CABRERA E S,IOST A,et al.Sliding wear of?-C:H coatings against alumina in corrosive media[J].Diamond&related materials,2013,38(17):139-147.
[16]GISPERT M P,SERRO A P,COLA?O R,et al.Wear of ceramic coated metal-on-metal bearings used for hip replacement[J].Wear,2007,263(7):1060-1065.
[17]ROSSI S,FEDRIZZI L,LEONI M,et al.(Ti,Cr)N and Ti/TiN PVD coatings on 304 stainless steel substrates:wear-corrosion behaviour[J].Thin solid films,1999350(1-2):161-167.
[18]HOSEINI M,JEDENMALM A,BOLDIZAR A.Tribological investigation of coatings for artificial joints[J].Wear,2008,264(11):958-966.
[19]李洪涛,蒋百灵,杨波,等.电场环境对磁控溅射纯Cr薄膜沉积过程的影响[J].功能材料,2010,41(11):2006-2009.LI Hong-tao,JIANG Bai-ling,YANG Bo,et al.Effect of electric field environment on the process of depositing pure Cr films by magnetron sputtering[J].Journal of functional materials,2010,41(11):2006-2009.
[20]李洪涛,蒋百灵,曹政.占空比对磁控溅射纯Cr镀层微观组织结构的影响[J].真空科学与技术学报,201030(2):133-137.LI Hong-tao,JIANG Bai-ling,CAO Zheng.Influence of duty cycle on microstructures of magnetron sputtered pure Cr coatings[J].Chinese journal of vacuum science and technology,2010,30(2):133-137.
[21]王珍,杨得全.一些金属、半导体和化合物的Ar+溅射产额[J].真空与低温,1990(3):51-56.WANG Zhen,YANG De-quan.Ar+sputtering yields of some metals,semiconductors and compounds[J].Vacuum and cryogenics,1990(3):51-56.
[22]赵升升,周晟昊,余红雅,等.厚度对TiN薄膜力学性能的影响[J].真空科学与技术学报,2016,36(3):291-295.ZHAO Sheng-sheng,ZHOU Sheng-hao,YU Hong-ya,et al.Effect of TiN filmsthickness on mechanical properties of stainless steel[J].Chinese journal of vacuum science and technology,2016,36(3):291-295.
[23]袁琳,高原,张维,等.负偏压对多弧离子镀TiN薄膜的影响[J].表面技术,2012,41(1):20-26.YUAN Lin,GAO Yuan,ZHANG Wei,et al.Effect of negative bias voltage on Ti N coating deposited by MAIP[J].Surface technology,2012,41(1):20-26.
[24]魏永强,张艳霞,文振华,等.脉冲偏压占空比对TiN/TiAlN多层薄膜微观结构和硬度的影响[J].表面技术,2014,43(1):1-6.WEI Yong-qiang,ZHANG Yan-xia,WEN Zhen-hua,et al.Effect of different pulse bias duty cycleon themicrostructure and hardness of TiN/TiAlN multilayer coatings[J].Surface technology,2014,43(1):1-6.
[25]WOKULSKI Z.Mechanical properties of TiN whiskers[J].Physica status solidi,2010,120(1):175-184.
[26]李成明,孙晓军,张增毅,等.ZrN及其多层膜的性质和耐腐蚀性能[J].材料热处理学报,2003,24(4):55-58.LI Cheng-ming,SUN Xiao-jun,ZHANG Zeng-yi,et al.Properties and corrosion resistant of ZrN and ZrN/TiNmultilayer films[J].Transactions of materials and heat treatment,2003,24(4):55-58.
[27]余存烨.锆与钛耐蚀性比较及应用互补性[J].腐蚀与防护,2007,28(5):223-226.YU Cun-ye.Comparison of corrosion resistance of zirconium and titanium and their complementarity in applications[J].Corrosion&protection,2007,28(5):223-226.