氩离子轰击对中频-直流磁控溅射铝薄膜耐蚀性能的影响
|
摘要
目的研究氩离子轰击这种后处理工艺对TC4钛合金表面铝膜层结构和耐蚀性能的影响,为飞机钛合金紧固件的表面腐蚀防护工作提供理论依据。方法首先采用中频-直流相结合的磁控溅射离子镀方法在Ti-6Al-4V钛合金(TC4)基体表面制备铝膜,通过电化学方法研究膜层厚度和腐蚀时间对耐蚀性能的影响规律。其次,采用氩离子轰击工艺对膜层进行后处理,探讨氩离子轰击对膜层耐蚀性能的影响,同时利用SEM、EDS、AFM表征界面形貌,并分析耐蚀机理。最后,通过显微硬度仪和微纳米划痕仪测试膜层表面硬度和界面结合性能。结果随着膜层厚度从11.1μm增加至15.9μm,自腐蚀电流密度下降了76.6%,而当厚度由15.9μm增加至20.3μm时,自腐蚀电流密度又下降了24.3%。腐蚀浸泡时间达到24 h时,腐蚀产物在疏松氧化膜内的累积和覆盖阻碍了膜层的腐蚀;在48～72 h时,随着铝膜层相对疏松的腐蚀产物逐渐脱落,腐蚀逐渐加剧;浸泡至96h时,涂层表面出现宏观腐蚀坑。氩离子轰击后,膜层表面粗糙度增加,铝膜层自腐蚀电流密度由未轰击时的1.65×10~(-8)A/cm~2大幅度降低至7.29×10~(-10)A/cm~2。结论随着铝膜层厚度的增加,膜层耐蚀性逐渐增强。膜层在浸泡初期和中期,均具有较强的耐腐蚀性能;浸泡后期,膜层逐渐发生点蚀,耐蚀性能下降。表面氩离子轰击后,膜层的耐蚀性能、显微硬度和界面结合性能显著提高。
The work aims to study the effect of argon ion bombardment on the structure and corrosion resistance of Al film on TC4 titanium alloy, and to provide theoretical basis for the surface corrosion protection of aeronautical titanium alloy fasteners. The Al film was prepared on the surface of Ti-6 Al-4 V(TC4) titanium alloy substrate by magnetron sputtering ion plating combined with middle frequency and direct current. The influence of film thickness and corrosion time on the corrosion resistance was studied by electrochemical method. In addition, with the post-treatment of the film by argon ion bombardment, the influence of argon ion bombardment on the corrosion resistance of Al film was explored, the SEM, EDS and AFM were used to characterize the interfacial morphology and to analyze the corrosion mechanism. The micro hardness tester and micro-nano scratch tester were applied to test the surface hardness and adhesion strength. With the increase of film thickness from 11.1 μm to 15.9 μm, the corrosion current density decreased about 76.6%, and when the thickness increased from 15.9 μm to 20.3 μm,the corrosion current density decreased by 24.3%. As the immersion time reached 24 h, the accumulation and coverage of corrosion products in the loose oxide film hindered the corrosion of the Al film. For 48～72 h, the corrosion of the Al film was aggravated gradually with the exfoliation of the relatively loose corrosion products. The macroscopic corrosion pits appeared on the surface of the film after 96 h. After Ar+ ion bombardment, the surface roughness increased, the self-corrosion current density of aluminum film decreased from 1.65×10~(-8)A/cm~2 to 7.29×10~(-8)A/cm~2. With the increase of the thickness of the aluminum film,the corrosion resistance is gradually enhanced. The film has strong corrosion resistance in the early and middle stages of immersion, and the pitting corrosion occurs in the film after later immersion stage, and the corrosion resistance of the film decreases. After argon ion bombardment, the corrosion resistance, microhardness and interfacial bonding properties of the film are improved.
The work aims to study the effect of argon ion bombardment on the structure and corrosion resistance of Al film on TC4 titanium alloy, and to provide theoretical basis for the surface corrosion protection of aeronautical titanium alloy fasteners. The Al film was prepared on the surface of Ti-6 Al-4 V(TC4) titanium alloy substrate by magnetron sputtering ion plating combined with middle frequency and direct current. The influence of film thickness and corrosion time on the corrosion resistance was studied by electrochemical method. In addition, with the post-treatment of the film by argon ion bombardment, the influence of argon ion bombardment on the corrosion resistance of Al film was explored, the SEM, EDS and AFM were used to characterize the interfacial morphology and to analyze the corrosion mechanism. The micro hardness tester and micro-nano scratch tester were applied to test the surface hardness and adhesion strength. With the increase of film thickness from 11.1 μm to 15.9 μm, the corrosion current density decreased about 76.6%, and when the thickness increased from 15.9 μm to 20.3 μm,the corrosion current density decreased by 24.3%. As the immersion time reached 24 h, the accumulation and coverage of corrosion products in the loose oxide film hindered the corrosion of the Al film. For 48～72 h, the corrosion of the Al film was aggravated gradually with the exfoliation of the relatively loose corrosion products. The macroscopic corrosion pits appeared on the surface of the film after 96 h. After Ar+ ion bombardment, the surface roughness increased, the self-corrosion current density of aluminum film decreased from 1.65×10~(-8)A/cm~2 to 7.29×10~(-8)A/cm~2. With the increase of the thickness of the aluminum film,the corrosion resistance is gradually enhanced. The film has strong corrosion resistance in the early and middle stages of immersion, and the pitting corrosion occurs in the film after later immersion stage, and the corrosion resistance of the film decreases. After argon ion bombardment, the corrosion resistance, microhardness and interfacial bonding properties of the film are improved.
引文
[1]刘培,王振玉,李晓伟,等.TC4钛合金表面Cr2AlC涂层的制备及高温氧化行为[J].表面技术,2016,45(11):16-22.LIU P,WANG Z Y,LI X W,et al.Preparation of Cr2Al Ccoatings on TC4 titanium alloy and its high-temperature oxidation behaviour[J].Surface technology,2016,45(11):16-22.
[2]李英亮.紧固件概论[M].北京:国防工业出版社,2014:1-16.LI Ying-liang.Fastners basics[M].Beijing:National Defense Industry Press,2014:1-16.
[3]林凯.TC4热浸镀Al-Zn及其在钛/铝合金接触腐蚀防护中的应用[D].南京:南京航空航天大学,2011.LIN K.TC4 hot-dip Al-Zn alloys coating on TC4 surface to prevent titanium/aluminum alloys galvanic corrosion[D].Nanjing:Nanjing University of Aeronautics and Astronautics,2011.
[4]MOURITZ A P.Introduction to aerospace materials[M].Cambridge:Woodhead Publishing,2012:203-223.
[5]蔡建明,弭光宝,高帆,等.航空发动机用先进高温钛合金材料技术研究与发展[J].材料工程,2016,44(8):1-10.CAI J M,MI G B,GAO F,et al.Research and development of some advanced high temperature titanium alloy for aero-engine[J].Journal of materials engineering,2016,44(8):1-10.
[6]吴松林,刘明辉,易俊兰,等.不同表面处理工艺对Ti-6A1-4V钛合金漆层结合力和电偶腐蚀性能影响[J].材料工程,2013(1):6-11.WU S L,LIU M H,YI J L,et al.Effects of different surface treatments on painting adhesion and galvanic corrosion behavior of titanium alloy Ti-6Al-4V[J].Journal of materials engineering,2013(1):6-11.
[7]万冰华,张松林,林忠亮,等.航空航天钛合金紧固件铝涂层评价指标及方法研究[J].航天标准化,2017(1):1-9.WAN B H,ZHANG S L,LIN Z L,et al.Study on evaluation index and method of aluminum coating for aerospace titanium alloy fastener[J].Aerospace standardization,2017(1):1-9.
[8]谢发勤,金石,严密林,等.离子镀铝的钛合金紧固件的耐蚀性能研究[J].西北工业大学学报,1995(1):147-150.XIE F Q,JIN S,YAN M L,et al.Study on corrosion resistance of ion-plated titanium alloy fasteners[J].Journal of Northwestern Polytechnical University,1995(1):147-150.
[9]胡芳,代明江,林松盛,等.循环氩离子轰击对磁控溅射铝膜结构和性能的影响[J].中国表面工程,2015,28(1):49-55.HU F,DAI M J,LIN S S,et al.Influences of cycles argon ion bombardment on structures and properties of Al films deposited by magnetron sputtering[J].China surface engineering,2015,28(1):49-55.
[10]陈亚军,黄彦,胡隆伟,等.中频-直流磁控溅射铝涂层微米压入特性及低温循环性能[J].中国表面工程,2017,30(1):83-92.CHEN Y J,HUANG Y,HU L W,et al.Micro-indentation and low-temperature cyclic properties of aluminum coating prepared by MF-DC magnetron sputtering[J].China surface engineering,2017,30(1):83-92.
[11]VITEZ I,KRUMES D,BUDI?I,et al.Properties and application of PVD coatings[J].World academy of science engineering&technology,2000,28(70):852.
[12]ALEXEEV O K,FATEEV V N.Application of the magnetron sputtering for nanostructured electrocatalysts synthesis[J].International journal of hydrogen energy,2016,41(5):3373-3386.
[13]WHEELER J M,WEHRS J,FAVARO G,et al.In-situ optical oblique observation of scratch testing[J].Surface&coatings technology,2014,258:127-133.
[14]BANDEIRA R M,DRUNEN J V,GARCIA A C,et al.Influence of the thickness and roughness of polyaniline coatings on corrosion protection of AA7075 aluminum alloy[J].Electrochimica acta,2017,240:215-224.
[15]CIGADA A,CABRINI M,PEDEFERRI P.Increasing of the corrosion resistance of the Ti6Al4V alloy by high thickness anodic oxidation[J].Journal of materials science materials in medicine,1992,3(6):408-412.
[16]WANG Z,LI J,WANG Y,et al.An EIS analysis on corrosion resistance of anti-abrasion coating[J].Surfaces&interfaces,2017,6:33-39.
[17]林玉划.纳米ZrO2复合水性环氧锌铝涂层的制备与性能研究[D].南京:南京航空航天大学,2016.LIN Y H.Preparation and properties of nano-ZrO2/waterborne epoxy zinc-aluminum composite coating[D].Nanjing:Nanjing University of Aeronautics and Astronautics,2016.
[18]OU Y X,LIN J,TONG S,et al.Structure,adhesion and corrosion behavior of CrN/TiN superlattice coatings deposited by the combined deep oscillation magnetron sputtering and pulsed dc magnetron sputtering[J].Surface&coatings technology,2016,293:21-27.
[2]李英亮.紧固件概论[M].北京:国防工业出版社,2014:1-16.LI Ying-liang.Fastners basics[M].Beijing:National Defense Industry Press,2014:1-16.
[3]林凯.TC4热浸镀Al-Zn及其在钛/铝合金接触腐蚀防护中的应用[D].南京:南京航空航天大学,2011.LIN K.TC4 hot-dip Al-Zn alloys coating on TC4 surface to prevent titanium/aluminum alloys galvanic corrosion[D].Nanjing:Nanjing University of Aeronautics and Astronautics,2011.
[4]MOURITZ A P.Introduction to aerospace materials[M].Cambridge:Woodhead Publishing,2012:203-223.
[5]蔡建明,弭光宝,高帆,等.航空发动机用先进高温钛合金材料技术研究与发展[J].材料工程,2016,44(8):1-10.CAI J M,MI G B,GAO F,et al.Research and development of some advanced high temperature titanium alloy for aero-engine[J].Journal of materials engineering,2016,44(8):1-10.
[6]吴松林,刘明辉,易俊兰,等.不同表面处理工艺对Ti-6A1-4V钛合金漆层结合力和电偶腐蚀性能影响[J].材料工程,2013(1):6-11.WU S L,LIU M H,YI J L,et al.Effects of different surface treatments on painting adhesion and galvanic corrosion behavior of titanium alloy Ti-6Al-4V[J].Journal of materials engineering,2013(1):6-11.
[7]万冰华,张松林,林忠亮,等.航空航天钛合金紧固件铝涂层评价指标及方法研究[J].航天标准化,2017(1):1-9.WAN B H,ZHANG S L,LIN Z L,et al.Study on evaluation index and method of aluminum coating for aerospace titanium alloy fastener[J].Aerospace standardization,2017(1):1-9.
[8]谢发勤,金石,严密林,等.离子镀铝的钛合金紧固件的耐蚀性能研究[J].西北工业大学学报,1995(1):147-150.XIE F Q,JIN S,YAN M L,et al.Study on corrosion resistance of ion-plated titanium alloy fasteners[J].Journal of Northwestern Polytechnical University,1995(1):147-150.
[9]胡芳,代明江,林松盛,等.循环氩离子轰击对磁控溅射铝膜结构和性能的影响[J].中国表面工程,2015,28(1):49-55.HU F,DAI M J,LIN S S,et al.Influences of cycles argon ion bombardment on structures and properties of Al films deposited by magnetron sputtering[J].China surface engineering,2015,28(1):49-55.
[10]陈亚军,黄彦,胡隆伟,等.中频-直流磁控溅射铝涂层微米压入特性及低温循环性能[J].中国表面工程,2017,30(1):83-92.CHEN Y J,HUANG Y,HU L W,et al.Micro-indentation and low-temperature cyclic properties of aluminum coating prepared by MF-DC magnetron sputtering[J].China surface engineering,2017,30(1):83-92.
[11]VITEZ I,KRUMES D,BUDI?I,et al.Properties and application of PVD coatings[J].World academy of science engineering&technology,2000,28(70):852.
[12]ALEXEEV O K,FATEEV V N.Application of the magnetron sputtering for nanostructured electrocatalysts synthesis[J].International journal of hydrogen energy,2016,41(5):3373-3386.
[13]WHEELER J M,WEHRS J,FAVARO G,et al.In-situ optical oblique observation of scratch testing[J].Surface&coatings technology,2014,258:127-133.
[14]BANDEIRA R M,DRUNEN J V,GARCIA A C,et al.Influence of the thickness and roughness of polyaniline coatings on corrosion protection of AA7075 aluminum alloy[J].Electrochimica acta,2017,240:215-224.
[15]CIGADA A,CABRINI M,PEDEFERRI P.Increasing of the corrosion resistance of the Ti6Al4V alloy by high thickness anodic oxidation[J].Journal of materials science materials in medicine,1992,3(6):408-412.
[16]WANG Z,LI J,WANG Y,et al.An EIS analysis on corrosion resistance of anti-abrasion coating[J].Surfaces&interfaces,2017,6:33-39.
[17]林玉划.纳米ZrO2复合水性环氧锌铝涂层的制备与性能研究[D].南京:南京航空航天大学,2016.LIN Y H.Preparation and properties of nano-ZrO2/waterborne epoxy zinc-aluminum composite coating[D].Nanjing:Nanjing University of Aeronautics and Astronautics,2016.
[18]OU Y X,LIN J,TONG S,et al.Structure,adhesion and corrosion behavior of CrN/TiN superlattice coatings deposited by the combined deep oscillation magnetron sputtering and pulsed dc magnetron sputtering[J].Surface&coatings technology,2016,293:21-27.