固溶处理对Mg-2.0Zn-0.5Zr-3.0Gd生物降解镁合金组织及耐腐蚀性能的影响
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摘要
采用金相显微镜(OM)、扫描电镜(SEM)、透射电镜(TEM)研究固溶处理温度对Mg-2.0Zn-0.5Zr-3.0Gd(质量分数,%)生物镁合金显微组织的影响,通过失重、析氢和电化学方法研究合金在模拟体液(SBF)中的耐腐蚀性能。结果表明:铸态合金中,第二相(Mg,Zn)3Gd在合金基体中呈网状分布。固溶处理温度在460～500℃时,合金的晶粒尺寸随温度的升高而逐渐增大,温度为480℃时,没有溶入基体的(Mg,Zn)3Gd相以颗粒状或长条状的形式存在于基体中,部分颗粒与α-Mg基体具有共格关系。随着固溶处理温度的升高,合金的腐蚀速率先减小后增大,固溶处理温度在480℃时,合金的耐腐蚀性能比铸态合金的有了较大的提高。在120 h的浸泡实验中,合金的腐蚀速率在最后24 h时逐渐趋于稳定。
The effects of temperatures on microstructure of Mg-2.0 Zn-0.5 Zr-3.0 Gd magnesium alloy were investigated by metallographic microscope(OM), scanning electronic microscope(SEM), transmission electron microscope(TEM).The corrosion properties of magnesium alloy were studied by mass loss, hydrogen evolution and electrochemical tests in the simulated body fluid(SBF). The results show that the second phase(Mg, Zn)3 Gd is network distributed in the alloy matrix for the as-cast alloy. The grain size of alloy gradually increases with the increase of solid solution temperature at a temperature range of 460-500 ℃. There is no dissolved(Mg, Zn)3 Gd phase present as a strip and particle form in alloy matrix when the temperature is 480 ℃. While partially granular phase has coherent interface relationship with α-Mg matrix. The corrosion rate for the solid solution alloy decreases with the increase of the solid solution temperature, and then increases. The corrosion resistance of the alloy is better than that of the as-cast alloy when the solid solution temperature is 480 ℃. In the immersion test of 120 h, the corrosion rate of alloys gradually reaches a steady state value in the last 24 h.
The effects of temperatures on microstructure of Mg-2.0 Zn-0.5 Zr-3.0 Gd magnesium alloy were investigated by metallographic microscope(OM), scanning electronic microscope(SEM), transmission electron microscope(TEM).The corrosion properties of magnesium alloy were studied by mass loss, hydrogen evolution and electrochemical tests in the simulated body fluid(SBF). The results show that the second phase(Mg, Zn)3 Gd is network distributed in the alloy matrix for the as-cast alloy. The grain size of alloy gradually increases with the increase of solid solution temperature at a temperature range of 460-500 ℃. There is no dissolved(Mg, Zn)3 Gd phase present as a strip and particle form in alloy matrix when the temperature is 480 ℃. While partially granular phase has coherent interface relationship with α-Mg matrix. The corrosion rate for the solid solution alloy decreases with the increase of the solid solution temperature, and then increases. The corrosion resistance of the alloy is better than that of the as-cast alloy when the solid solution temperature is 480 ℃. In the immersion test of 120 h, the corrosion rate of alloys gradually reaches a steady state value in the last 24 h.
引文
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[16]ZHANG X,WU Y,XUE Y,WANG Z,YANG L.Biocorrosion behavior and cytotoxicity of a Mg-Gd-Zn-Zr alloy with long period stacking ordered structure[J].Materials Letters,2012,86:42-45.
[17]YANG L,HUANG Y,FEYERABEND F,WILLUMEIT R,MENDIS C,KAINER K U,HORT N.Microstructure,mechanical and corrosion properties of Mg-Dy-Gd-Zr alloys for medical application[J].Acta Biomaterialia,2013,9(10):8499-8508.
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[20]章晓波,殷俏,马青龙,巴志新,王章忠,王强.时效处理对挤压态Mg-Gd-Nd-Sr-Zn-Zr合金力学与腐蚀性能的影响[J].中国有色金属学报,2016,26(3):526-534.ZHANG Xiao-bo,YIN Qiao,MA Qing-long,BA Zhi-xin,WANG Zhang-zhong,WANG Qiang.Effect of aging treatment on mechanical and corrosion properties of as-extruded Mg-Gd-Nd-Sr-Zn-Zr alloy[J].The Chinese Journal of Nonferrous Metals,2016,26(3):526-534.
[21]SHI Z M,LIU M,ATRENS A.Measurement of the corrosion rate of magnesium alloys using Tafel extrapolation[J].Corrosion Science,2010,52:579-588.
[22]ABIDIN N I Z,ATRENS A D,MARTIN D,ATRENS A.Corrosion of high purity Mg,Mg2Zn0.2Mn,ZE41 and AZ91in Hank`s solution at 37℃[J].Corrosion Science,2011,53:3542-3556.
[23]HE Z,FU P,WU Y,PENG L,ZHANG Y,LI Z.High cycle fatigue behavior of as-cast Mg96.34Gd2.5Zn1Zr0.16 alloy fabricated by semi-continuous casting[J].Materials Science and Engineering A,2013,587:72-78.
[24]ZHANG J,ZHANG W,BIAN L,CHENG W,NIU X,XU C,WU S.Study of Mg-Gd-Zn-Zr alloys with long period stacking ordered structures[J].Materials Science&Engineering A,2013,585:268-276.
[25]汤伊金,章桢彦,靳丽,董杰,丁文江.Mg-Gd系合金时效析出研究进展[J].中国有色金属学报,2014,24(1):8-24.TANG Yi-jin,ZHANG Zhen-yuan,JIN Li,DONG Jie,DING Wen-jiang.Research progress on ageing precipitation of Mg-Gd alloys[J].The Chinese Journal of Nonferrous Metals,2014,24(1):8-24.
[26]黄孝瑛.材料微观结构的电子显微学分析[M].北京:冶金工业出版社,2008:484-486.HUANG Xiao-ying.The microstructure of materials and its electron microscopy analysis[M].Beijng:Metallurgical Industry Press,2008:484-486.
[27]XU C,ZHENG M Y,WU K,WANG E D,FAN G H,XU SW,KAMADO S,LIU X D,WANG G J,LüX Y,LI M J,LIU Y T.Effect of final rolling reduction on the microstructure and mechanical properties of Mg-Gd-Y-Zn-Zr alloy sheets[J].Materials Science&Engineering A,2013,559:232-240.
[28]章晓波,袁光银,王章忠.铸造镁合金Mg-Nd-Zn-Zr的生物腐蚀性能[J].中国有色金属学报,2013,23(4):905-911.ZHANG Xiao-bo,YUAN Guang-yin,WANG Zhang-zhong.Biocorrosion properties of as-cast Mg-Nd-Zn-Zr magnesium alloy[J].The Chinese Journal of Nonferrous Metals,2013,23(4):905-911.
[29]ZHANG X,BA Z,WANG Z,XUE Y.Microstructures and corrosion behavior of biodegradable Mg-6Gd-x Zn-0.4Zr alloys with and without long period stacking ordered structure[J].Corrosion Science,2016,105:68-77.
[30]GUI Z,KAN Z,LI Y.Mechanical and corrosion properties of Mg-Gd-Zn-Zr-Mn biodegradable alloy by hot extrusion[J].Journal of Alloys and Compounds,2016,685:222-230.
[31]CAO F,SHI Z,SONG G,LIU M,MATTHEW S D,ATRENS A.Influence of hot rolling on the corrosion behavior of several Mg-X alloys[J].Corrosion Science,2015,90:176-191.
[2]张佳,宗阳,袁广银,常建卫,付鹏怀,丁文江.新型医用Mg-Nd-Zn-Zr镁合金在模拟体液中的降解行为[J].中国有色金属学报,2010,20(10):1989-1997.ZHANG Jia,ZONG Yang,YUAN Guang-yin,CHANGJian-wei,FU Peng-huai,DING Wen-jiang.Degradable behavior of new-type medical Mg-Nd-Zn-Zr magnesium alloy in simulated body fluid[J].The Chinese Journal of Nonferrous Metals,2010,20(10):1989-1997.
[3]LI J,TAN L,WAN P,YU X,YANG K.Study on microstructure and properties of extruded Mg-2Nd-0.2Zn alloy as potential biodegradable implant material[J].Materials Science and Engineering C,2015,49:422-429.
[4]袁广银,章晓波,牛佳林,陶海荣,陈道运,何耀华,蒋垚,丁文江.新型可降解生物医用镁合金JDBM的研究进展[J].中国有色金属学报,2011,21(10):2476-2488.YUAN Guang-yin,ZHANG Xiao-bo,NIU Jia-lin,TAOHai-rong,CHEN Dao-yun,HE Yao-hua,JIANG Yao,DINGWen-jiang.Research progress of new type of degradable biomedical magnesium alloys JDBM[J].The Chinese Journal of Nonferrous Metals,2011,21(10):2476-2488.
[5]YANG L,HUANG Y,FEYERABEND F,WILLUMEIT R,MENDIS C,KAINER K U,HORT N.Microstructure,mechanical and corrosion properties of Mg-Dy-Gd-Zr alloys for medical applications[J].Acta Biomaterialia,2013,9(10):8499-8508.
[6]BROOKS E K,DER S,EHRENSBERGER M T.Corrosion and mechanical performance of AZ91 exposed to simulated inflammatory conditions[J].Materials Science&Engineering C,2016,60:427-436.
[7]ZHANG B,HOU Y,WANG X,WANG Y,GENG L.Mechanical properties,degradation performance and cytotoxicity of Mg-Zn-Ca biomedical alloys with different compositions[J].Materials Science and Engineering C,2011,31:1667-1673.
[8]ZHANG E,YANG L.Microstructure,mechanical properties and bio-corrosion properties of Mg-Zn-Mn-Ca alloy for biomedical application[J].Materials Science&Engineering A,2008,497:111-118.
[9]王鲁宁,孟瑶,刘丽君,董超芳,岩雨.可降解锌基生物材料的研究进展[J].金属学报,2017,53(10):1317-1322.WANG Lu-ning,MENG Yao,LIU Li-jun,DONG Chao-fang,YAN Yu.Research progress on biodegradable zinc-based biomaterials[J].Acta Metallurgica Sinca,2017,53(10):1317-1322.
[10]GU X,ZHENG Y,CHENG Y,ZHONG S,XI T.In vitro corrosion and biocompatibility of binary magnesium alloys[J].Biomaterials,2009,30:484-498.
[11]袁广银,牛佳林.可降解医用镁合金在骨修复应用中的研究进展[J].金属学报,2017,53(10):1169-1180.YUAN Guang-yin,NIU Jia-lin.Research progress of biodegradable magnesium alloys for orthopedic applications[J].Acta Metallurgica Sinica,2017,53(10):1169-1180.
[12]HOU X,CAO Z,ZHAO L,WANG L,WU Y,WANG L.Microstructure,texture and mechanical properties of a hot rolled Mg-6.5Gd-1.3Nd-0.7Y-0.3Zn alloy[J].Materials and Design,2012,37:776-781.
[13]HUANG S,WANG J,HOU F,HUANG X,PAN F.Effect of Gd and Y contents on the microstructural evolution of long period stacking ordered phase and the corresponding mechanical properties in Mg-Gd-Y-Zn-Mn alloys[J].Materials Science&Engineering A,2014,612:363-370.
[14]FEYERABEND F,FISCHER J,HOLTZ J,WITTE F,WILLUMEIT R,DRüCKER H,VOGT C,HORT N.Evaluation of short-term effects of rare earth and other elements used in magnesium alloys on primary cells and cell lines[J].Acta Biomaterialia,2010,6:1834-1842.
[15]ZHANG X,BA Z,WANG Q,WU Y,WANG Z,WANG Q.Uniform corrosion behavior of GZ51K alloy with long period stacking ordered structure for biomedical application[J].Corrosion Science,2014,88:1-5.
[16]ZHANG X,WU Y,XUE Y,WANG Z,YANG L.Biocorrosion behavior and cytotoxicity of a Mg-Gd-Zn-Zr alloy with long period stacking ordered structure[J].Materials Letters,2012,86:42-45.
[17]YANG L,HUANG Y,FEYERABEND F,WILLUMEIT R,MENDIS C,KAINER K U,HORT N.Microstructure,mechanical and corrosion properties of Mg-Dy-Gd-Zr alloys for medical application[J].Acta Biomaterialia,2013,9(10):8499-8508.
[18]PARK B K,JUN J H,KIM M.Influence of Zn addition on aging response and corrosion resistance of Mg-Gd-Nd-Zr alloy[J].Materials Transactions,2008,49(5):931-935.
[19]LIU S J,YANG G Y,LUO S F,JIE W Q.Microstructure and mechanical properties of san mold cast Mg-4.58Zn-2.6Gd-0.18Zr magnesium alloy after different heat treatments[J].Journal of Alloys and Compounds,2015,644:846-853.
[20]章晓波,殷俏,马青龙,巴志新,王章忠,王强.时效处理对挤压态Mg-Gd-Nd-Sr-Zn-Zr合金力学与腐蚀性能的影响[J].中国有色金属学报,2016,26(3):526-534.ZHANG Xiao-bo,YIN Qiao,MA Qing-long,BA Zhi-xin,WANG Zhang-zhong,WANG Qiang.Effect of aging treatment on mechanical and corrosion properties of as-extruded Mg-Gd-Nd-Sr-Zn-Zr alloy[J].The Chinese Journal of Nonferrous Metals,2016,26(3):526-534.
[21]SHI Z M,LIU M,ATRENS A.Measurement of the corrosion rate of magnesium alloys using Tafel extrapolation[J].Corrosion Science,2010,52:579-588.
[22]ABIDIN N I Z,ATRENS A D,MARTIN D,ATRENS A.Corrosion of high purity Mg,Mg2Zn0.2Mn,ZE41 and AZ91in Hank`s solution at 37℃[J].Corrosion Science,2011,53:3542-3556.
[23]HE Z,FU P,WU Y,PENG L,ZHANG Y,LI Z.High cycle fatigue behavior of as-cast Mg96.34Gd2.5Zn1Zr0.16 alloy fabricated by semi-continuous casting[J].Materials Science and Engineering A,2013,587:72-78.
[24]ZHANG J,ZHANG W,BIAN L,CHENG W,NIU X,XU C,WU S.Study of Mg-Gd-Zn-Zr alloys with long period stacking ordered structures[J].Materials Science&Engineering A,2013,585:268-276.
[25]汤伊金,章桢彦,靳丽,董杰,丁文江.Mg-Gd系合金时效析出研究进展[J].中国有色金属学报,2014,24(1):8-24.TANG Yi-jin,ZHANG Zhen-yuan,JIN Li,DONG Jie,DING Wen-jiang.Research progress on ageing precipitation of Mg-Gd alloys[J].The Chinese Journal of Nonferrous Metals,2014,24(1):8-24.
[26]黄孝瑛.材料微观结构的电子显微学分析[M].北京:冶金工业出版社,2008:484-486.HUANG Xiao-ying.The microstructure of materials and its electron microscopy analysis[M].Beijng:Metallurgical Industry Press,2008:484-486.
[27]XU C,ZHENG M Y,WU K,WANG E D,FAN G H,XU SW,KAMADO S,LIU X D,WANG G J,LüX Y,LI M J,LIU Y T.Effect of final rolling reduction on the microstructure and mechanical properties of Mg-Gd-Y-Zn-Zr alloy sheets[J].Materials Science&Engineering A,2013,559:232-240.
[28]章晓波,袁光银,王章忠.铸造镁合金Mg-Nd-Zn-Zr的生物腐蚀性能[J].中国有色金属学报,2013,23(4):905-911.ZHANG Xiao-bo,YUAN Guang-yin,WANG Zhang-zhong.Biocorrosion properties of as-cast Mg-Nd-Zn-Zr magnesium alloy[J].The Chinese Journal of Nonferrous Metals,2013,23(4):905-911.
[29]ZHANG X,BA Z,WANG Z,XUE Y.Microstructures and corrosion behavior of biodegradable Mg-6Gd-x Zn-0.4Zr alloys with and without long period stacking ordered structure[J].Corrosion Science,2016,105:68-77.
[30]GUI Z,KAN Z,LI Y.Mechanical and corrosion properties of Mg-Gd-Zn-Zr-Mn biodegradable alloy by hot extrusion[J].Journal of Alloys and Compounds,2016,685:222-230.
[31]CAO F,SHI Z,SONG G,LIU M,MATTHEW S D,ATRENS A.Influence of hot rolling on the corrosion behavior of several Mg-X alloys[J].Corrosion Science,2015,90:176-191.