占空比对5005铝合金赤泥等离子体电解氧化复合陶瓷层结构和性能的影响探究
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摘要
目的探究正负脉冲占空比对5005铝合金表面赤泥(RM)等离子体电解氧化(PEO)复合陶瓷层的生长机制、组织结构和抗腐蚀性能的影响。方法以赤泥为电解液添加剂,采用PEO技术,以不同正负占空比配比在5005铝合金表面制备陶瓷层,利用X射线衍射仪(XRD)、附带能谱仪(EDS)的扫描电镜(SEM)和电化学工作站,测试和表征陶瓷层的物相组成、微观形貌和成分以及抗腐蚀性能。结果单独升高正、负占空比,电流均增大,击穿放电作用加强,赤泥颗粒扩散速率和参与成膜的浓度增加,陶瓷层生长速度加快,厚度增大,颜色变深,受负占空比的影响比较明显,反应时间为20 min时,厚度最大分别可达27.70μm和35.82μm。陶瓷层主要由γ-Al_2O_3组成,并含有少量的无定形相、α-Al_2O_3以及赤泥矿物相Fe_2O_3、CaCO_3和SiO_2,其中α-Al_2O_3和Fe_2O_3含量随负占空比的升高而快速增加,最多可分别达到6.40%和2.86%。陶瓷层的致密性和抗腐蚀性能随正负占空比的升高,均先增加后降低,但负占空比的影响较正占空比的大,当正占空比为28%～42%和负占空比为12%～18%时,陶瓷层的结构致密,腐蚀电流密度和腐蚀速率小,阻抗大,抗腐蚀性能好。结论 PEO陶瓷层的组织结构和性能受正占空比的影响较负占空比的小,适当的正负占空比配比可获得结构致密、抗腐蚀性能好的赤泥PEO复合陶瓷层。
The work aims to study the effects of various positive and negative duty cycles on the growth mechanism,structure and corrosion resistance of red mud(RM)plasma electrolytic oxidation(PEO)composite ceramic coatings on 5005 aluminum alloy surface.The ceramic coatings were prepared on the surface of 5005 aluminum alloy at various positive and negative duty cycles with RM as electrolyte additive by PEO technology.Phase composition,microstructure,constitution and corrosion resistance of ceramic coating were tested and characterized with X-ray diffractometer(XRD),scanning electron microscope(SEM)with energy disperse spectrometer(EDS)and electrochemical workstation.When the positive or negative duty cycle was increased separately,the current increased and the breakdown discharge function improved.With the increase of diffusion rate of RM particles and the concentration in the coating formation,the ceramic coating grew faster with higher thickness and darker color,but was significantly affected by the negative duty cycle.When the reaction time was 20 min,the maximum thickness could be 27.70μm and 35.82μm,respectively.The coating consisted mainly ofγ-Al_2O_3 and a small percentage of amorphous phase,α-Al_2O_3 and RM minerals including Fe_2O_3,CaCO_3 and SiO_2.α-Al_2O_3 and Fe_2O_3 went up rapidly with the increase of negative duty cycle,which could be up to 6.40%and 2.86%,respectively.With the increase of duty cycle,the coating compactness and corrosion resistance firstly increased and then decreased,but the effect of negative duty cycle was greater than that of positive duty cycle.When the positive duty cycle was 24%～42%and negative duty cycle was 12%～18%,the coating was compact with smaller corrosion current density and corrosion rate,and larger impedance,showing a good corrosion resistance.The structures and properties of PEO coatings are affected by positive duty cycle less than by negative duty cycle,and a RM-PEO composite coating with dense structure and good corrosion resistance can be fabricated by proper proportion of positive and negative duty cycles.
The work aims to study the effects of various positive and negative duty cycles on the growth mechanism,structure and corrosion resistance of red mud(RM)plasma electrolytic oxidation(PEO)composite ceramic coatings on 5005 aluminum alloy surface.The ceramic coatings were prepared on the surface of 5005 aluminum alloy at various positive and negative duty cycles with RM as electrolyte additive by PEO technology.Phase composition,microstructure,constitution and corrosion resistance of ceramic coating were tested and characterized with X-ray diffractometer(XRD),scanning electron microscope(SEM)with energy disperse spectrometer(EDS)and electrochemical workstation.When the positive or negative duty cycle was increased separately,the current increased and the breakdown discharge function improved.With the increase of diffusion rate of RM particles and the concentration in the coating formation,the ceramic coating grew faster with higher thickness and darker color,but was significantly affected by the negative duty cycle.When the reaction time was 20 min,the maximum thickness could be 27.70μm and 35.82μm,respectively.The coating consisted mainly ofγ-Al_2O_3 and a small percentage of amorphous phase,α-Al_2O_3 and RM minerals including Fe_2O_3,CaCO_3 and SiO_2.α-Al_2O_3 and Fe_2O_3 went up rapidly with the increase of negative duty cycle,which could be up to 6.40%and 2.86%,respectively.With the increase of duty cycle,the coating compactness and corrosion resistance firstly increased and then decreased,but the effect of negative duty cycle was greater than that of positive duty cycle.When the positive duty cycle was 24%～42%and negative duty cycle was 12%～18%,the coating was compact with smaller corrosion current density and corrosion rate,and larger impedance,showing a good corrosion resistance.The structures and properties of PEO coatings are affected by positive duty cycle less than by negative duty cycle,and a RM-PEO composite coating with dense structure and good corrosion resistance can be fabricated by proper proportion of positive and negative duty cycles.
引文
[1]STOJADINOVIC S.Plasma electrolytic oxidation of metals[J].Journal of the Serbian Chemical Society,2013,78(5):713-716.
[2]MOON S,JEONG Y.Generation mechanism of microdischarges during plasma electrolytic oxidation of Al in aqueous solutions[J].Corrosion science,2009,51(7):1506-1512.
[3]STOJADINOVIC S,VASILIC R,BELCA I,et al.Characterization of the plasma electrolytic oxidation of aluminium in sodium tungstate[J].Corrosion science,2010,52(10):3258-3265.
[4]WHITE L,KOO Y,NERALLA S,et al.Enhanced mechanical properties and increased corrosion resistance of a biodegradable magnesium alloy by plasma electrolytic oxidation(PEO)[J].Materials science&engineering B,Solid-state materials for advanced technology,2016,208:39.
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[6]LU S F,LOU B S,YANG Y C,et al.Effects of duty cycle and electrolyte concentration on the microstructure and biocompatibility of plasma electrolytic oxidation treatment on zirconium metal[J].Thin solid films,2015,596:87-93.
[7]BABAEI M,DEHGHANIAN C,TAHERI P,et al.Effect of duty cycle and electrolyte additive on photocatalytic performance of TiO2-ZrO2,composite layers prepared on CP Ti by micro arc oxidation method[J].Surface&coatings technology,2016,307:554-564.
[8]JAIN V K,CHAUHAN A S,THAKUR A,et al.Fabrication of micro tools and micro patterns by electrochemical microoamachining and some investigation into overpotential[J].Journal of advanced manufacturing systems,2013,12(2):85-106.
[9]芦笙,吴良文,徐荣远,等.正脉冲占空比对ZK60镁合金微弧氧化陶瓷膜的影响[J].材料保护,2010,43(9):39-41.LU Sheng,WU Liang-wen,XU Rong-yuan,et al.Influence of positive duty cycle on micro-arc oxidation ceramic coating of ZK60 magnesium alloy[J].Materials protection,2010,43(9):39-41.
[10]赵晖,朱其柱,万智来,等.脉冲占空比对钛合金微弧氧化膜及电流密度的影响[J].电镀与精饰,2011,33(2):34-36.ZHAO Hui,ZHU Qi-zhu,WAN Zhi-lai,et al.Effect of duty cycle on film and current density of pulse micro-arc oxidation on titanium alloy[J].Plating and finishing,2011,33(2):34-36.
[11]NASIRIVATAN H,EBRAHIMI-KAHRIZSANGI R,ASGARANI M K.Tribological performance of PEO-WCnanocomposite coating on Mg alloys deposited by plasma electrolytic oxidation[J].Tribology international,2016,98:253-260.
[12]张玉林,于佩航,韦银河,等.石墨烯添加剂对铝合金表面微弧氧化膜耐磨耐蚀性的影响[J].材料热处理学报,2017,38(8):103-109.ZHANG Yu-lin,YU Pei-hang,WEI Yin-he,et al.Influence of graphene additvie on wear resistance and corrosion resistance of micro acr oxidation coating formed on LY12aluminum alloy surface[J].Transactions of materials and heat treatment,2017,38(8):103-109.
[13]WANG P,WU T,XIAO Y T,et al.Effect of Al2O3 micro-powder additives on the properties of micro-arc oxidation coatings formed on 6061 aluminum alloy[J].Journal of materials engineering&performance,2016,25(9):1-5.
[14]VAKILIAZGHANDI M,FATTAHALHOSSEINI A,KES-HAVARZ M.Effects of Al2O3 nano-particles on corrosion performance of plasma electrolytic oxidation coatings formed on 6061 aluminum alloy[J].Journal of materials engineering&performance,2016,25(12):5302-5313.
[15]索相波,马世宁,邱骥,等.纳米Si O2复合处理对7A52铝合金微弧氧化陶瓷层孔隙率及性能的影响[J].航空材料学报,2009,29(6):66-69.SUO Xiang-bo,MA Shi-ning,QIU Ji,et al.Improving of surface lporosity and properties of MAO ceramic coatings by incorporation of SiO2 nanoparticles[J].Journal of aeronautical materials,2009,29(6):66-69.
[16]吴德凤,雷源源,张晓燕,等.纳米Si O2添加剂对铸造铝铜合金微弧氧化陶瓷层耐磨性的影响[J].表面技术,2013,42(5):42-44.WU De-feng,LEI Yuan-yuan,ZHANG Xiao-yan,et al.Effect of nano-SiO2 additives on the microstructure and wear resistance of micro-arc oxidation ceramics coating on casting aluminum alloy[J].Surface technology,2013,42(5):42-44.
[17]ANTUNES M L P,COUPERTHWAITE S J,CONCEIC-AO F T D.Red mud from brazil:thermal behavior and physical properties[J].Industrial&engineering chemistry research,2012,51(2):775-779.
[18]SGLAVO V M,CAMPOSTRINI R,MAURINA S.Bauxite'red mud'in the ceramic industry.Part 1:Thermal behaviour[J].Journal of the European Ceramic Society,2000,20(3):235-244.
[19]COLLAZO A,COVELO A,NOVOA X R,et al.Corrosion protection performance of sol-gel coatings doped with red mud applied on AA2024-T3[J].Progress in organic coatings,2012,74(2):334-342.
[20]COLLAZO A,FEMANDEZ D,IZQUIERDO M,et al.Evaluation of red mud as surface treatment for carbon steel prior painting[J].Progress in organic coatings,2005,52(4):351-358.
[21]PEREZ-VILLAREJO L,CORPAS-IGLESIAS F A,MAR-TINEZ-MARTINEZ,et al.Manufacturing new ceramic materials from clay and red mud derived from the aluminium industry[J].Construction&building materials,2012,35(10):656-665.
[22]CHUNG F H.Quantitative interpretation of X-ray diffraction patterns of mixtures.I.Matrix-flushing method for quantitative multicomponent analysis[J].Journal of applied crystallography,1974,7(6):7.
[23]CHUNG F H.Quantitative interpretation of X-ray diffraction patterns of mixtures.II.Adiabatic principle of X-ray diffraction analysis of mixtures[J].Journal of applied crystallography,1974,7(6):6.
[24]刘荣明,郭锋,李鹏飞.电压对铝合金微弧氧化陶瓷层形成的影响[J].材料热处理学报,2008,29(1):137-140.LIU Rong-ming,GUO Feng,LI Peng-fei.Effect of voltage on formation of ceramic coating prepared by micro-arc oxidation on aluminum alloy[J].Transaction of materials and heat treatment,2008,29(1):137-140.
[25]郭锋,刘荣明,李鹏飞.电压参数对铝合金微弧氧化陶瓷层相组成的影响[J].金属热处理,2007,32(10):38-40.GUO Feng,LIU Rong-ming,LI Peng-fei.Effect of voltage parameters on phase constitution of ceramic coating prepared by micro-arc oxidation on aluminum alloy[J].Heat treatment of metals,2007,32(10):38-40.
[26]王虹斌,方志刚,蒋百灵.微弧氧化技术及其在海洋环境中的应用[M].北京:国防工业出版社,2010.WANG Hong-bin,FANG Zhi-gang,JIANG Bai-ling.Microarc oxidation technology and its applications in sea environments[M].Beijing:National Defense Industry Press,2010.
[27]李均明.铝合金微弧氧化陶瓷层的形成机制及其磨损性能[D].西安:西安理工大学,2008.LI Jun-ming.Formation mechanism and abrasion tests of micro-arc oxidation ceramic layers on aluminum alloy[D].Xi'an:Xi'an University of Technology,2008.
[28]LIU Shi-feng,ZENG Jian-min.Effects of negative voltage on microstructure and corrosion resistance of red mud plasma electrolytic oxidation coatings[J].Surface and coatings technology,2018,352:15-25.
[29]周雅,江溢民,周佳.反向占空比对铝合金微弧氧化膜组织结构和耐蚀性能的影响[J].材料保护,2012,45(1):33-35.ZHOU Ya,JIANG Yi-min,ZHOU Jia.Effect of reverse duty cycle on microstructure and corrosion resistance of micro-arc oxidation coating on aluminum alloy[J].Materials protection,2012,45(1):33-35.
[30]赵玉峰,杨世彦,韩明武.等离子体微弧氧化技术及其发展[J].材料导报,2006,20(6):102-104.ZHAO Yu-feng,YANG Shi-yan,HAN Ming-wu.Technique of plasma microarc oxidation and its development[J].Materials review,2006,20(6):102-104.
[31]时海芳,李晓,吕文涛,等.铝合金陶瓷涂层的研究进展[J].表面技术,2007,36(6):74-76.SHI Hai-fang,LI Xiao,LV Wen-tao,et al.Progress of aluminum alloy ceramic coating[J].Surface technology2007,36(6):74-76.
[32]STERN M,GEABY A L.Electrochemical polarization[J].Journal of the electrochemical society,1957,104(1):56.
[33]曹楚南,张鉴清.电化学阻抗谱导论[M].北京:科学出版社,2002.CAO Chu-nan,ZHANG Jian-qing.Introduction to electrochemical impedance spectroscopy[J].Beijing:Science Press,2002.
[34]CHVEDOV D,OSTAP S,LE T.Surface properties of red mud particles from potentiometric titration[J].Colloids&surfaces A physicochemical&engineering aspects,2001182(1):131-141.
[35]CABEZA M,COLLAZO A,NOVOA X R,et al.Red mud as a corrosion inhibitor for reinforced concrete[J].Journal of corrosion science&engineering,2003(6):1016.
[2]MOON S,JEONG Y.Generation mechanism of microdischarges during plasma electrolytic oxidation of Al in aqueous solutions[J].Corrosion science,2009,51(7):1506-1512.
[3]STOJADINOVIC S,VASILIC R,BELCA I,et al.Characterization of the plasma electrolytic oxidation of aluminium in sodium tungstate[J].Corrosion science,2010,52(10):3258-3265.
[4]WHITE L,KOO Y,NERALLA S,et al.Enhanced mechanical properties and increased corrosion resistance of a biodegradable magnesium alloy by plasma electrolytic oxidation(PEO)[J].Materials science&engineering B,Solid-state materials for advanced technology,2016,208:39.
[5]陈喜娣,蔡启舟,尹荔松.占空比对6061铝合金微弧氧化膜层结构与耐蚀性的影响[J].特种铸造及有色合金,2011,31(7):671-675.CHEN Xi-di,CAI Qi-zhou,YIN Li-song.Effect of pulse duty cycles on structure and corrosion resistance of microarc oxidation films on 6061 Al alloy[J].Special casting&nonferrous alloys,2011,31(7):671-675.
[6]LU S F,LOU B S,YANG Y C,et al.Effects of duty cycle and electrolyte concentration on the microstructure and biocompatibility of plasma electrolytic oxidation treatment on zirconium metal[J].Thin solid films,2015,596:87-93.
[7]BABAEI M,DEHGHANIAN C,TAHERI P,et al.Effect of duty cycle and electrolyte additive on photocatalytic performance of TiO2-ZrO2,composite layers prepared on CP Ti by micro arc oxidation method[J].Surface&coatings technology,2016,307:554-564.
[8]JAIN V K,CHAUHAN A S,THAKUR A,et al.Fabrication of micro tools and micro patterns by electrochemical microoamachining and some investigation into overpotential[J].Journal of advanced manufacturing systems,2013,12(2):85-106.
[9]芦笙,吴良文,徐荣远,等.正脉冲占空比对ZK60镁合金微弧氧化陶瓷膜的影响[J].材料保护,2010,43(9):39-41.LU Sheng,WU Liang-wen,XU Rong-yuan,et al.Influence of positive duty cycle on micro-arc oxidation ceramic coating of ZK60 magnesium alloy[J].Materials protection,2010,43(9):39-41.
[10]赵晖,朱其柱,万智来,等.脉冲占空比对钛合金微弧氧化膜及电流密度的影响[J].电镀与精饰,2011,33(2):34-36.ZHAO Hui,ZHU Qi-zhu,WAN Zhi-lai,et al.Effect of duty cycle on film and current density of pulse micro-arc oxidation on titanium alloy[J].Plating and finishing,2011,33(2):34-36.
[11]NASIRIVATAN H,EBRAHIMI-KAHRIZSANGI R,ASGARANI M K.Tribological performance of PEO-WCnanocomposite coating on Mg alloys deposited by plasma electrolytic oxidation[J].Tribology international,2016,98:253-260.
[12]张玉林,于佩航,韦银河,等.石墨烯添加剂对铝合金表面微弧氧化膜耐磨耐蚀性的影响[J].材料热处理学报,2017,38(8):103-109.ZHANG Yu-lin,YU Pei-hang,WEI Yin-he,et al.Influence of graphene additvie on wear resistance and corrosion resistance of micro acr oxidation coating formed on LY12aluminum alloy surface[J].Transactions of materials and heat treatment,2017,38(8):103-109.
[13]WANG P,WU T,XIAO Y T,et al.Effect of Al2O3 micro-powder additives on the properties of micro-arc oxidation coatings formed on 6061 aluminum alloy[J].Journal of materials engineering&performance,2016,25(9):1-5.
[14]VAKILIAZGHANDI M,FATTAHALHOSSEINI A,KES-HAVARZ M.Effects of Al2O3 nano-particles on corrosion performance of plasma electrolytic oxidation coatings formed on 6061 aluminum alloy[J].Journal of materials engineering&performance,2016,25(12):5302-5313.
[15]索相波,马世宁,邱骥,等.纳米Si O2复合处理对7A52铝合金微弧氧化陶瓷层孔隙率及性能的影响[J].航空材料学报,2009,29(6):66-69.SUO Xiang-bo,MA Shi-ning,QIU Ji,et al.Improving of surface lporosity and properties of MAO ceramic coatings by incorporation of SiO2 nanoparticles[J].Journal of aeronautical materials,2009,29(6):66-69.
[16]吴德凤,雷源源,张晓燕,等.纳米Si O2添加剂对铸造铝铜合金微弧氧化陶瓷层耐磨性的影响[J].表面技术,2013,42(5):42-44.WU De-feng,LEI Yuan-yuan,ZHANG Xiao-yan,et al.Effect of nano-SiO2 additives on the microstructure and wear resistance of micro-arc oxidation ceramics coating on casting aluminum alloy[J].Surface technology,2013,42(5):42-44.
[17]ANTUNES M L P,COUPERTHWAITE S J,CONCEIC-AO F T D.Red mud from brazil:thermal behavior and physical properties[J].Industrial&engineering chemistry research,2012,51(2):775-779.
[18]SGLAVO V M,CAMPOSTRINI R,MAURINA S.Bauxite'red mud'in the ceramic industry.Part 1:Thermal behaviour[J].Journal of the European Ceramic Society,2000,20(3):235-244.
[19]COLLAZO A,COVELO A,NOVOA X R,et al.Corrosion protection performance of sol-gel coatings doped with red mud applied on AA2024-T3[J].Progress in organic coatings,2012,74(2):334-342.
[20]COLLAZO A,FEMANDEZ D,IZQUIERDO M,et al.Evaluation of red mud as surface treatment for carbon steel prior painting[J].Progress in organic coatings,2005,52(4):351-358.
[21]PEREZ-VILLAREJO L,CORPAS-IGLESIAS F A,MAR-TINEZ-MARTINEZ,et al.Manufacturing new ceramic materials from clay and red mud derived from the aluminium industry[J].Construction&building materials,2012,35(10):656-665.
[22]CHUNG F H.Quantitative interpretation of X-ray diffraction patterns of mixtures.I.Matrix-flushing method for quantitative multicomponent analysis[J].Journal of applied crystallography,1974,7(6):7.
[23]CHUNG F H.Quantitative interpretation of X-ray diffraction patterns of mixtures.II.Adiabatic principle of X-ray diffraction analysis of mixtures[J].Journal of applied crystallography,1974,7(6):6.
[24]刘荣明,郭锋,李鹏飞.电压对铝合金微弧氧化陶瓷层形成的影响[J].材料热处理学报,2008,29(1):137-140.LIU Rong-ming,GUO Feng,LI Peng-fei.Effect of voltage on formation of ceramic coating prepared by micro-arc oxidation on aluminum alloy[J].Transaction of materials and heat treatment,2008,29(1):137-140.
[25]郭锋,刘荣明,李鹏飞.电压参数对铝合金微弧氧化陶瓷层相组成的影响[J].金属热处理,2007,32(10):38-40.GUO Feng,LIU Rong-ming,LI Peng-fei.Effect of voltage parameters on phase constitution of ceramic coating prepared by micro-arc oxidation on aluminum alloy[J].Heat treatment of metals,2007,32(10):38-40.
[26]王虹斌,方志刚,蒋百灵.微弧氧化技术及其在海洋环境中的应用[M].北京:国防工业出版社,2010.WANG Hong-bin,FANG Zhi-gang,JIANG Bai-ling.Microarc oxidation technology and its applications in sea environments[M].Beijing:National Defense Industry Press,2010.
[27]李均明.铝合金微弧氧化陶瓷层的形成机制及其磨损性能[D].西安:西安理工大学,2008.LI Jun-ming.Formation mechanism and abrasion tests of micro-arc oxidation ceramic layers on aluminum alloy[D].Xi'an:Xi'an University of Technology,2008.
[28]LIU Shi-feng,ZENG Jian-min.Effects of negative voltage on microstructure and corrosion resistance of red mud plasma electrolytic oxidation coatings[J].Surface and coatings technology,2018,352:15-25.
[29]周雅,江溢民,周佳.反向占空比对铝合金微弧氧化膜组织结构和耐蚀性能的影响[J].材料保护,2012,45(1):33-35.ZHOU Ya,JIANG Yi-min,ZHOU Jia.Effect of reverse duty cycle on microstructure and corrosion resistance of micro-arc oxidation coating on aluminum alloy[J].Materials protection,2012,45(1):33-35.
[30]赵玉峰,杨世彦,韩明武.等离子体微弧氧化技术及其发展[J].材料导报,2006,20(6):102-104.ZHAO Yu-feng,YANG Shi-yan,HAN Ming-wu.Technique of plasma microarc oxidation and its development[J].Materials review,2006,20(6):102-104.
[31]时海芳,李晓,吕文涛,等.铝合金陶瓷涂层的研究进展[J].表面技术,2007,36(6):74-76.SHI Hai-fang,LI Xiao,LV Wen-tao,et al.Progress of aluminum alloy ceramic coating[J].Surface technology2007,36(6):74-76.
[32]STERN M,GEABY A L.Electrochemical polarization[J].Journal of the electrochemical society,1957,104(1):56.
[33]曹楚南,张鉴清.电化学阻抗谱导论[M].北京:科学出版社,2002.CAO Chu-nan,ZHANG Jian-qing.Introduction to electrochemical impedance spectroscopy[J].Beijing:Science Press,2002.
[34]CHVEDOV D,OSTAP S,LE T.Surface properties of red mud particles from potentiometric titration[J].Colloids&surfaces A physicochemical&engineering aspects,2001182(1):131-141.
[35]CABEZA M,COLLAZO A,NOVOA X R,et al.Red mud as a corrosion inhibitor for reinforced concrete[J].Journal of corrosion science&engineering,2003(6):1016.