镁合金表面CaF_2/MgF_2复合膜层的制备及降解行为
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摘要
为改善镁合金的耐蚀性能,采用化学沉积法在AZ31镁合金表面制备了微-纳级别尺度CaF_2/MgF_2复合膜层,分析该复合膜层的形貌、成分及相结构。采用Hank’s仿生溶液中浸泡和电化学测试技术,结合浸泡过程中膜层EIS谱和表面形貌成分的变化,研究CaF_2/MgF_2复合膜层的体外降解行为。结果表明:该复合膜层外层为纳米尺度的片状CaF_2晶体,内层为致密的MgF_2转化膜。CaF_2膜层提高了单一氟转化层的自腐蚀电位φcorr和极化电阻Rp,浸泡13 d后其电荷转移电阻仍维持在1×10~4Ω·cm~2以上。试样在Hank’s溶液中浸泡7 d后CaF_2膜层发生局部溶解;9 d后在CaF_2层局部脱落处,Cl-渗透到MgF_2膜层而发生点蚀。
CaF_2/MgF_2 composite film was prepared on AZ31 magnesium alloy by chemical treatment to improve its corrosion resistance. The morphology and composition of the composite film were analyzed. The evolution of electrochemical impedance spectroscope(EIS) patterns and the change of the surface appearance and chemical composition of the composite film in Hank's solutions were investigated to study the degradation process of film. The results show that the composite film consists of nanoscale flaky-like CaF_2 crystals in out layer and compact MgF_2 conversion film in inner layer. The corrosion potential φcorr and polarization resistance Rp of the fluorine conversion layer are improved by the CaF_2 film. And the Rct of the composite coating after 13 d immersion in Hank's solution is still above1×10~4 Ω·cm~2. CaF_2 dissolves partially and adsorbs some of phosphate ions after 7 d immersion in Hank's solution. After9 d immersion, pitting corrosions occur because of the partial exfoliation of CaF_2 film and the infiltration of Cl-into the MgF_2 film.
CaF_2/MgF_2 composite film was prepared on AZ31 magnesium alloy by chemical treatment to improve its corrosion resistance. The morphology and composition of the composite film were analyzed. The evolution of electrochemical impedance spectroscope(EIS) patterns and the change of the surface appearance and chemical composition of the composite film in Hank's solutions were investigated to study the degradation process of film. The results show that the composite film consists of nanoscale flaky-like CaF_2 crystals in out layer and compact MgF_2 conversion film in inner layer. The corrosion potential φcorr and polarization resistance Rp of the fluorine conversion layer are improved by the CaF_2 film. And the Rct of the composite coating after 13 d immersion in Hank's solution is still above1×10~4 Ω·cm~2. CaF_2 dissolves partially and adsorbs some of phosphate ions after 7 d immersion in Hank's solution. After9 d immersion, pitting corrosions occur because of the partial exfoliation of CaF_2 film and the infiltration of Cl-into the MgF_2 film.
引文
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[2]SEZER N,EVIS Z,KAYHAN S M,TAHMASEBIFAR A,KO?M.Review of magnesium-based biomaterials and their applications[J].Journal of Magnesium&Alloys,2018,6(1):23-43.
[3]HORNBERGER H,VIRTANEN S,BOCCACCINI A R.Biomedical coatings on magnesium alloys-A review[J].Acta Biomaterialia,2012,8(7):2442-2455.
[4]ERINC M,SILLEKENS W H,MANNENS R,WERKHOVEN R J.Applicability of existing magnesium alloys as biomedical implant materials[J].Magnesium Technology,2009:209-214.
[5]WANG Z L,GUO Y.Corrosion resistance and adhesion of poly(L-lactic acid)/Mg F2,composite coating on AZ31magnesium alloy for biomedical application[J].Russian Journal of Non-Ferrous Metals,2016,57(4):381-388.
[6]YAN T T,TAN L L,XIONG D S,LIU X J,ZHANG B C,YANG K.Fluoride treatment and in vitro corrosion behavior of an AZ31B magnesium alloy[J].Materials Science and Engineering C,2010,30(5):740-748.
[7]LI Q,LIU X J,WANG Z Q,YAN T T,TAN L L,ZHANG BC,YANG K.Biocompatibility and antibacterial property of fluoride coating on AZ31B magnesium alloy[J].Chinese Journal of Materials Research,2011,25(2):193-198.
[8]JIANG H,WANG J,CHEN M,LIU D.Biological activity evaluation of magnesium fluoride coated Mg-Zn-Zr alloy in vivo[J].Materials Science and Engineering C,2017,75:1068-1074.
[9]SUN W,ZHANG G,TAN L,YANG K,AI H.The fluoride coated AZ31B magnesium alloy improves corrosion resistance and stimulates bone formation in rabbit model[J].Materials Science and Engineering C,2016,63:506-511.
[10]ZHANG C Y,GAO J C,LIU C L.Effect of fluoride treatment on corrosion property of AZ31 magnesium alloy in Hank’s solution[J].Advanced Materials Research,2011,239/242(33):186-190.
[11]吉建新,朱彤.氟化钙骨内植入的生物学评价[J].实用口腔医学杂志,1997(3):184-186.JI Jian-xin,ZHU Tong.Biological evaluation of calcium fluoride intraosseous implantation[J].Journal of Practical Stomatology,1997(3):184-186.
[12]XU H H,MOREAU J L,SUN L,CHOW L C.Strength and fluoride release characteristics of a calcium fluoride based dental nanocomposite[J].Biomaterials,2008,29(32):4261-4267.
[13]吉建新.氟化钙直接盖髓的疗效观察[J].中华生物医学工程杂志,1996(2):141-142.JI Jian-xin.Calcium fluoride directly covered pulp[J].Journal of Modern Clinical Medical Bioengineering,1996(2):141-142.
[14]邓甫.纤维素/碱土金属氟化物复合材料的制备、性能与形成机理研究[D].北京:北京林业大学,2016.DENG Fu.Research on preparation,properties,and fabrication mechanism of cellulose/alkaline earth metal fluoride composites[D].Beijing:Beijing Forestry University,2016.
[15]YI H,REHMAN F U,ZHAO C Q,LIU B,HE N Y.Recent advances in nano scaffolds for bone repair[J].Bone Research,2016,4(4):206-216.
[16]ZHANG R,WAN Y,AI X,WANG T,MEN B.Preparation of micro-nanostructure on titanium implants and its bioactivity[J].Transactions of Nonferrous Metals Society of China,2016,26(4):1019-1024.
[17]ZHANG J,GU Y H,GUO Y J,NING C Y.Electrochemical behavior of biocompatible AZ31 magnesium alloy in simulated body fluid[J].Journal of Materials Science,2012,47(13):5197-5204.
[18]SASIKUMAR Y,SOLOMON M M,OLASUNKANMI L O,EBENSO E E.Effect of surface treatment on the bioactivity and electrochemical behavior of magnesium alloys in simulated body fluid[J].Materials&Corrosion,2017,68(7):776-790.
[19]WANG Z L,YAN Y H,WAN T,YANG H.Poly(L-lactic acid)/hydroxyapatite/collagen composite coatings on AZ31magnesium alloy for biomedical application[J].Proc Inst Mech Eng H,2013,227(10):1094-103.
[20]曹楚南、张鉴清.电化学阻抗谱导论[M].北京:科学出版社,2002:154-164.CAO Chu-nan,ZHANG Jian-qing.An introduction to electrochemical impedance spectroscopy[M].Beijing:Science Press,2002:154-164.
[21]张春艳,柳歆鹏,黄佳祈,刘成龙,杨惠,杨有利.镁合金表面氟转化层降解过程的电化学阻抗谱[J].中国有色金属学报,2015,25(2):401-407.ZHANG Chun-yan,LIU Xin-peng,HUANG Jia-qi,LIUCheng-long,YANG Hui,YANG You-li.Degradation process of fluorine conversion coating on magnesium alloy by electrochemical impedance spectroscopy[J].The Chinese Journal of Nonferrous Metals,2015,25(2):401-407.
[22]FU L H,DONG C F,LI X G,HAN W.Electrochemical behaviors of magnesium alloy with phosphate conversion coating in NaCl solutions[J].Rare Metals,2016,35(10):747-757.
[23]李绮,刘新杰,颜廷亭,谭丽丽,张炳春,杨柯.氟处理对AZ31B镁合金生物耐蚀降解行为的影响[J].稀有金属材料与工程,2011,40(10):1859-1863.LI Qi,LIU Xin-jie,YAN Ting-ting,TAN Li-li,ZHANGBing-chun,YANG Ke.Effect of fluoride conversion treatment on bio-corrosion behavior of AZ31B magnesium alloy[J].Rare Metal Materials and Engineering,2011,40(10):1859-1863.
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