AZ91镁合金生物活性钙系磷化膜的制备及性能研究
|
摘要
目前，临床上广泛应用的临床骨植入材料主要是不锈钢，钛和铬基合金。但是，这些材料密度大，与人体骨的弹性模量不匹配，造成应力屏蔽，而且属于重金属元素，难降解，需要二次手术取出，对人的身心健康造成不好的影响，而且二次手术加重经济负担。另一方面，这些金属材料密度大，其弹性模量与人体骨相差很大，造成应力屏蔽效应，对骨的生长产生不利的影响。当前，开始对镁合金作为骨植入材料进行研究。镁合金具有密度小，具有良好的力学性能，比强度高，与人体骨弹性模量接近，易降解性等优点。但是镁合金的化学性质活泼，耐蚀性不好，所以要提高它的耐蚀性。另一方面，要在镁合金表面镀一层具有生物活性的膜，促进骨生长。
本论文采用钙系磷化液在镁合金AZ91表面制备具有生物活性的钙系磷化膜。采用控制变量法，在其它条件都不变的情况下，加入不同含量的间硝基苯磺酸钠、钼酸钠以及不同的pH值制备出磷化膜。采用扫描电镜观察磷化膜的表面形貌，极化曲线分析它的耐腐蚀性。得出结论，间硝基苯磺酸钠具有促进成膜的作用，但是含量过多的时候也影响成膜质量，影响耐腐蚀性。钼酸钠具有增加形核质点的作用，促进成膜，过多含量的钼酸钠在溶液中形成难溶的钼酸钙，降低钙离子含量，影响成膜。再次，通过实验研究证明，pH值对成膜也有极大的影响。当pH值为2.5以下时，膜的质量很差，由于酸度太大，镁合金腐蚀速度过快，成膜的速度小于腐蚀速度，使膜层覆盖不均匀,但是当溶液的pH过高的时候，成膜速度慢，导致晶粒粗大，影响膜层的耐蚀性能。经过以上实验得出最佳实验配方为氧化钙10g/L，磷酸60ml/L,硝酸钙10g/L,间硝基苯磺酸钠2g/L,钼酸钠1g/L,pH为3.0，温度40℃。
采用能谱分析，得到膜层的化学成分，原子含量百分比，可以看出磷化膜的主要成分是钙系磷酸盐。采用xrd对膜层进行衍射分析，确定物相，得出膜的主要成分是磷酸钙。
另一方面，本论文研究了磷化膜的成膜机理。在不同的反应时间下，10s，30s，60s，2min，5min，10min，20min，30min，得到膜层，对其进行扫描电镜观察，分析其显微组织，得出钙系磷化膜首先在β相上形成成核质点，逐渐向α相上扩展。刚开始时快速成膜阶段，然后经历缓慢成膜，最后超过30min时，磷化膜出现动态平衡阶段，镁基体腐蚀的速度和成膜的速度相平衡，对其耐腐蚀性也影响不大，所以最佳成膜时间是30min。
At present, the clinical bone implant materials are mainly stainless steel, titaniumand chrome base alloy. But, these materials’ density, and elastic modulus don’tmatch with human bone.And because these materials belong to heavy metal，itcontains heavy metal elements,it’s bad to people’s health。. the refractory, need totake out a second time and need a surgery.It has bad effect to physical and mentalhealth and a second surgery increase economic burden. On the other hand, these metalmaterials’ density, the elastic modulus are very different from the human bone, and itcause stress shielding effect and make the growth of bone slowly. At present,magnesium alloy material began to have been used as bone implant for study.Magnesium alloy has the small density, good mechanical properties, high strength,close to human body bone elastic modulus, easily degradable, etc. But the chemiscalproperty of the magnesium alloy is live, the corrosion resistance is poor, so itscorrosion resistance needs to be improved. On the other hand, a layer of coating, onthe surface of magnesium alloys with biological activity of membrane can promotebone growth.
This thesis is about preparing bioactive calcium phosphate film in the liquid ofcalcium phosphate on the surface of AZ91surface。The method is controlling thevariable. under the condition ovariable in other conditions constant, join differentcontents of nitrobenzene between sulfonic acid sodium, sodium molybdate and indifferent pH value the preparation phosphating film. With scanning electronmicroscopy (sem) of phosphating film surface morphology, polarization curveanalysis its corrosion resistance.The conclusion were that the difficulties betweensulfonic acid sodium can promote the role of film, but much more content alsoinfluence the quality of film, affect corrosion resistance. Sodium molybdate increasednuclear particle shape, promote the film。 too much of the content of sodiummolybdate in solution formed undissolved molybdenum acid calcium, reduce thecalcium ion content, affects the film. Again, through the experiment proves that the pH value of film also have the enormous influence. When the pH value of2.5thefollowing, the film's quality was poor, the acidity because too big, magnesium alloycorrosion speed too fast, the speed of the film is less than the corrosion rate, make themembrane layer on the map.
From the energy spectrum analysis, it’s included that the membrane of thechemical composition, and atom percentage content, the main components of thephosphate film is calcium phosphate. By XRD on membrane layer diffraction analysis,object is determined, it is concluded that the main components of the film is calciumphosphate.
On the other hand, this paper studies the formation mechanism of phosphate film.In different reaction time,10s,30s,60s,2min,5min,10min,20min,30min, toget membrane layer, and carry on the scanning electron microscopy (SEM) of theanalysis of the microstructure, draw of calcium phosphate film first formed on thebeta phase into nuclear particle, α gradually to expand on that. It’s included that,phosphate film appear dynamic balance stage more than30min, magnesium matrixcorrosion speed and film speed phase equilibrium stage, the corrosion resistance andthe impact is not big, so the best film time is30min.
本论文采用钙系磷化液在镁合金AZ91表面制备具有生物活性的钙系磷化膜。采用控制变量法，在其它条件都不变的情况下，加入不同含量的间硝基苯磺酸钠、钼酸钠以及不同的pH值制备出磷化膜。采用扫描电镜观察磷化膜的表面形貌，极化曲线分析它的耐腐蚀性。得出结论，间硝基苯磺酸钠具有促进成膜的作用，但是含量过多的时候也影响成膜质量，影响耐腐蚀性。钼酸钠具有增加形核质点的作用，促进成膜，过多含量的钼酸钠在溶液中形成难溶的钼酸钙，降低钙离子含量，影响成膜。再次，通过实验研究证明，pH值对成膜也有极大的影响。当pH值为2.5以下时，膜的质量很差，由于酸度太大，镁合金腐蚀速度过快，成膜的速度小于腐蚀速度，使膜层覆盖不均匀,但是当溶液的pH过高的时候，成膜速度慢，导致晶粒粗大，影响膜层的耐蚀性能。经过以上实验得出最佳实验配方为氧化钙10g/L，磷酸60ml/L,硝酸钙10g/L,间硝基苯磺酸钠2g/L,钼酸钠1g/L,pH为3.0，温度40℃。
采用能谱分析，得到膜层的化学成分，原子含量百分比，可以看出磷化膜的主要成分是钙系磷酸盐。采用xrd对膜层进行衍射分析，确定物相，得出膜的主要成分是磷酸钙。
另一方面，本论文研究了磷化膜的成膜机理。在不同的反应时间下，10s，30s，60s，2min，5min，10min，20min，30min，得到膜层，对其进行扫描电镜观察，分析其显微组织，得出钙系磷化膜首先在β相上形成成核质点，逐渐向α相上扩展。刚开始时快速成膜阶段，然后经历缓慢成膜，最后超过30min时，磷化膜出现动态平衡阶段，镁基体腐蚀的速度和成膜的速度相平衡，对其耐腐蚀性也影响不大，所以最佳成膜时间是30min。
At present, the clinical bone implant materials are mainly stainless steel, titaniumand chrome base alloy. But, these materials’ density, and elastic modulus don’tmatch with human bone.And because these materials belong to heavy metal，itcontains heavy metal elements,it’s bad to people’s health。. the refractory, need totake out a second time and need a surgery.It has bad effect to physical and mentalhealth and a second surgery increase economic burden. On the other hand, these metalmaterials’ density, the elastic modulus are very different from the human bone, and itcause stress shielding effect and make the growth of bone slowly. At present,magnesium alloy material began to have been used as bone implant for study.Magnesium alloy has the small density, good mechanical properties, high strength,close to human body bone elastic modulus, easily degradable, etc. But the chemiscalproperty of the magnesium alloy is live, the corrosion resistance is poor, so itscorrosion resistance needs to be improved. On the other hand, a layer of coating, onthe surface of magnesium alloys with biological activity of membrane can promotebone growth.
This thesis is about preparing bioactive calcium phosphate film in the liquid ofcalcium phosphate on the surface of AZ91surface。The method is controlling thevariable. under the condition ovariable in other conditions constant, join differentcontents of nitrobenzene between sulfonic acid sodium, sodium molybdate and indifferent pH value the preparation phosphating film. With scanning electronmicroscopy (sem) of phosphating film surface morphology, polarization curveanalysis its corrosion resistance.The conclusion were that the difficulties betweensulfonic acid sodium can promote the role of film, but much more content alsoinfluence the quality of film, affect corrosion resistance. Sodium molybdate increasednuclear particle shape, promote the film。 too much of the content of sodiummolybdate in solution formed undissolved molybdenum acid calcium, reduce thecalcium ion content, affects the film. Again, through the experiment proves that the pH value of film also have the enormous influence. When the pH value of2.5thefollowing, the film's quality was poor, the acidity because too big, magnesium alloycorrosion speed too fast, the speed of the film is less than the corrosion rate, make themembrane layer on the map.
From the energy spectrum analysis, it’s included that the membrane of thechemical composition, and atom percentage content, the main components of thephosphate film is calcium phosphate. By XRD on membrane layer diffraction analysis,object is determined, it is concluded that the main components of the film is calciumphosphate.
On the other hand, this paper studies the formation mechanism of phosphate film.In different reaction time,10s,30s,60s,2min,5min,10min,20min,30min, toget membrane layer, and carry on the scanning electron microscopy (SEM) of theanalysis of the microstructure, draw of calcium phosphate film first formed on thebeta phase into nuclear particle, α gradually to expand on that. It’s included that,phosphate film appear dynamic balance stage more than30min, magnesium matrixcorrosion speed and film speed phase equilibrium stage, the corrosion resistance andthe impact is not big, so the best film time is30min.
引文
[1]陈先华，肖瑞，丁雪征等.AZ系镁合金研究现状[J].热加工工艺.2012,6(8):14-19.
[2] XN Gu, W Zheng, Y Cheng, YF Zheng. A study on alkaline heattreated Mg–Caalloy for the control of the biocorrosion rate. Acta Biomaterialia,2009,5:2790-2799.
[3]RZ Zhu. Corrosion of Metal [J]. Beijing: Metallurgical Industry Press,1993
[4]D L Albright. In: Paris H G, Hunt W H eds., Advances in Magnesium Alloys andComposites, Phoenix, Arizona: Internatioal Magnesium Association and theNon-ferrous Metals Committee, TMS,1988:48.
[5] X L Wu. Institute of Corrosion and Protection of Metals [J]. The ChineseAcademy of Science,1999.
[6]李高林，文九巴，贺俊光等.稀土Y对AZ80镁合金组织及耐蚀性能的影响[J].材料热处理学报.2012,(2):20-25.
[7].WQ Zhou, DY Shan, EH Han, et al. Structure and formation mechanism ofphosphate conversion coating on die-cast AZ91D magnesium alloy [J]. CorrosSci,2008,50(2):319-327.
[8]牛丽媛.镁合金锌系复合磷化膜成膜机理-微观结构及性能的研究[D].长春：吉林大学，2006.
[9]Kuwahara H, Al-Abdullat Y, Mazaki N, et al, Precipitation of magnesium apatiteon pure magnesium surface during immersing in Hank’s solution. Mater Trans,2001,42:1317-1321.
[10]金华兰，危仁杰，杨湘杰.镁合金磷酸盐转化膜层生长过程及其腐蚀率[J].特种铸造及有色合金，2005，25(11)：651-653.
[11]Dyugulu O, Kaya RA, Oktay G, et al. Investigation on the potential of magnesiumalloy AZ31as a bone implant. Mater Sci Forum,2007,421:546549.
[12]金华兰. ZM5镁合金磷酸盐表面改性处理技术[R].南昌：南昌大学，2005，7.
[13]David, Hawke, and D.L. Al bright. A phosphate permanganate conversion coatingfor magnesium[J].Metal Finishing,1995,10:34-38.
[14]曹洪志，邹振宇，陈波等.过共晶铝硅镁合金的研究现状及发展趋势[C].2012(第22届)重庆市铸造年会论文集.重庆大学材料科学与工程学院.国家镁合金材料工程技术研究中心.
[15] GY Li, JS Lian, LY Niu, et al. Growth of zinc phosphate coatings on AZ91Dmagnesium alloy, Surf Coat Technol,2006,201:1814-1820.
[16] D L Albright. Relationship of microstructures and corrosion behavior inmagnesium alloy ingots and castings [J]. Advances in magnesium alloys andcomposites,1988,8:60.
[17]M. Khosro Aghayani, B. Niroum. Effects of ultrasonic treatment onmicrostructure and tensile strength of AZ91magnesium alloy Original ResearchArticle[J]. Journal of Alloys and Compounds, Volume509, Issue1,5January2011, Pages114-122.
[18]徐开东.镁合金高能表面强化研究[D]武汉：华中科技大学，2010.
[19]Mohammad Reza Elahi, Mahmoud Heydarzadeh Sohi. Grain growth kinetics ofbulk AZ31magnesium alloy by hot pressing Original Research Article[J]. Journalof Alloys and Compounds, Volume527,25June2012, Pages193-196.
[20]刘燕，卢国龙，刘金丹，李亮.AZ91D镁合金表面电沉积n-ZrO_2/Ni复合镀层及耐蚀性研究[J].功能材料.2012,2(24):45-49.
[21]沟引宁，李鑫洋.表面活性剂对镁合金浸锌的影响[J].表面技术.2012，2(11):55-60.
[22] GY Li, JS Lian, LY Niu, et al. Growth of zinc phosphate coatings on AZ91Dmagnesium alloy [J]. Surf&Coatings Technol,2006,201(3/4):1814-1820.
[23]Cheng Zhong, Fan Liu, Yating Wu, Jingjing Le, Lei Liu, Meifeng He, Jiacai Zhu,Wenbin Hu. Liquid phase surface alloying of AZ91D magnesium alloy with Aland Ni powders Original Research Article[J]. Journal of Alloys and Compounds,Volume520,15April2012, Pages11-21.
[24] LY Niu, ZH Jiang, GY Li, et al. A study and application of zinc phosphatecoating on AZ91D magnesium alloy, Surf Coat Technology,2006,200:3021-3026.
[25]陈福文，余琨，陈良建等.Mg-6%Zn-10%(β-Ca3(PO4)2复合材料的制备及腐蚀降解行为[J].中国有色金属学报.2012，11(52):120-125.
[26] Unigovski Y B, Gutman E M. Surface Morphology of a Diecast Mg Alloy[J].Applied Surface Science,1999,153(1):47-52.
[27]宋诗哲.腐蚀电化学研究方法[M].北京：化学工业出版社，1988.
[28]徐淑强AZ91D镁合金环保型磷化膜制备技术、微观结构及其耐腐蚀性能研究[D]重庆：西南大学，2009.
[29]李新凯，张治民，赵亚丽.变形镁合金的研究现状及前景[J].热加工工艺.2011，25(53):142-146.
[30] XM Chen, GY Li, JS Lian, et al. Study of the formation and growth of tannicacid based conversion coating on AZ91D magnesium alloy. Surf Coat Technol,2009,204:736-747.
[31]钟丽应.稀土元素对AZ91镁合金组织结构和腐蚀行为的影响[J].浙江大学,2008.
[32]王芬.AZ31镁合金表面有机膜的耐蚀性能[J].特种铸造机有色合金.2011.35(24)：1104-1109
[33]HoungYuHsiao，Wen TaTsai.CharaeteriZationofanodiefilmsfor medon AZ9LdMagnesium alloy [J].Surface&Coatings Technology，2005，190:299-308.
[34] CL Wen,S K Guan,L Peng, et al. Characterization and degradation behavior ofAZ31alloy surface modified by bone-like hydroxyapatite for implant applications.App Surf Sci,2009,255:6433-6438.
[35]姜鹏. AZ91D镁合金表面化学转化及溶胶—凝胶技术制备复合涂层研究[J].哈尔滨哈尔滨工程大学,2007.
[36]崔作兴，顾云飞，邵忠才等.镁合金化学转化膜的制备及其性能研究[J].分子科学学报.2012,2(26):50-55.
[37]LP Xu, PC Feng, GN Yu, L Yang, et al. In vitro and in vivo evaluation of thesurface bioactivity of a calcium phosphate coated magnesium alloy[J].Biomaterials,2009,30:1512-1523.
[38]A. Dhanapal, S. Rajendra Boopathy, V. Balasubramanian. The Influence ofMechanical Surface Treatments on Fatigue Behavior of Extruded AZ61Magnesium Alloy Original Research Article[J]. Materials Science andEngineering: A, In Press, Accepted Manuscript, Available online12April2012
[39]游丽英.镁合金表面锌系磷化膜制备工艺及性能研究[D]长春：吉林大学，2007
[40]蒋晓军，陈昌国，刘瑜萍等.稀土强化镁合金耐蚀性能的研究进展[J].腐蚀与防护.2012,10(14):88-92.
[41]T.S. Srivatsan, C. Godbole, M. Paramsothy, M. Gupta. Hydrogen sorptionkinetics of magnesium hydride enhanced by the addition of Zr8Ni21alloyOriginal Research Article[J]. Journal of Alloys and Compounds, In Press,Accepted Manuscript, Available online30March2012.
[42]刘正.镁合金压铸及其铸件低周疲劳行为与裂纹扩展的研究[D].沈阳:中国科学院金属研究所，2001，15-17.
[43]CH Ye, YF Zheng, SQ Wang, TF Xi, YD Li. Low Cycle Fatigue Behavior ofAZ91D Magnesium Alloy Containing Rare-Earth Ce Element Original ResearchArticle[J]. Procedia Engineering, Volume27,2012, Pages1794-1800.
[44]赵磊，钟辉，龚国辉.镁合金的激光表面处理技术[J].轻合金加工技术.2012,6(41):90-95.
[45]YB Ren,H Wang,JJ Huang, et al, Study of biodegradation of pure magnesium.Key Eng Mater,2007,342.343:601-604.
[46]李光玉.镁合金表面有机涂层和化学镀层的研究[D]长春：吉林大学，2006.
[47]S.A. Pighin, G. Capurso, S. Lo Russo, H.A. Peretti. The Improved Performanceof a Mg-Rich Epoxy Coating on AZ91D Magnesium Alloy by Silane PretreatmentOriginal Research Article[J]. Corrosion Science, In Press, Accepted Manuscript,Available online3April2012.
[48]王晓明，查吉利，陈敏强等.压铸高危镁合金废料回收技术与设备研发[J].特种铸造及有色合金.2011，35(24)：1114-1119.
[49]X Wang, LX Hu, K Liu, YL Zhang.Influence of pH value, chloride ionconcentration and immersion time on corrosion rate of friction stir welded AZ61Amagnesium alloy weldments Review Article[J]. Journal of Alloys and Compounds,Volume523,15May2012, Pages49-60.
[50]雷作鍼，胡梦珍编译.金属的磷化处理[M].北京：机械工业出版社，1992
[51]尚伟，温玉清，李秀广等.AZ91D镁合金微弧氧化电参数对其耐蚀性的影响[J].表面技术.2012(2):10-14
[52]Md. Shahnewaz Bhuiyan, Yoshiharu Mutoh, A.J. McEvily. The role of aluminumoxide particulate reinforcements on cyclic fatigue and final fracture behavior of anovel magnesium alloy Original Research Article[J]. Materials Science andEngineering: A, Volume532,15January2012, Pages196-211.
[53]牛丽媛.镁合金锌系复合磷化膜成膜机理微观结构及性能的研究[D].长春：吉林大学，2006.
[54]陶军，龙思远，刘瑜等.镁合金有机涂层体系研究现状及发展趋势[J].热加工工艺.2011,25(53):133-137.
[55]S. Amira, J. Huot. Effect of cold rolling on hydrogen sorption properties ofdie-cast and as-cast magnesium alloys Original Research Article[J]. Journal ofAlloys and Compounds, Volume520,15April2012, Pages287-294.
[56]周婉秋，单大勇，曾荣昌等.镁合金的腐蚀行为与表面防护方法[J].材料
[57]]钱苗根姚寿山张少宗编著现代表面技术.[M].北京：机械工业出版社，2002
[58]周勇，熊金平，李依旋.PH和时间对镁合金表面磷化膜形貌和耐蚀性的影响[J].电镀与精饰.2012，7(4)：63-68.
[59]RG Hu, S Zhang, JF Bu, CJ Lin, GL Song. The Types and DistributionCharacterization of Al-Mn Phases in the AZ61Magnesium Alloy OriginalResearch Article[J]. Procedia Engineering, Volume27,2012, Pages833-839.
[60]A. Fabre, J.E. Masse. Magnesium alloys as body implants: Fracture mechanismunder dynamic and static loadings in a physiological environment OriginalResearch Article[J]. Acta Biomaterialia, Volume8, Issue2, February2012, Pages916-923.
[61]JF FAN,ZY CHEN, WD YANG, S FANG, BS XU. In vitro corrosion andbiocompatibility study of phytic acid modified WE43magnesium alloy OriginalResearch Article[J]. Applied Surface Science, Volume258, Issue8,1February2012, Pages3420-3427.
[62]Christopher A. Walton, Holly J. Martin, M.F. Horstemeyer, Paul T. Wang.Preparation and Characterization of Phosphate Film for Magnesium Alloy AZ31Original Research Article[J]. Physics Procedia, Volume25,2012, Pages194-199.
[63]刘瑜，龙思远，张小红，曾聪.AZ61镁合金的差热分析及凝固组织观察[C].2012(第22届)重庆市铸造年会论文集.重庆大学材料科学与工程学院.国家镁合金材料工程技术研究中心.
[64]MB YANG, FS PAN. Quantification of corrosion mechanisms under immersionand salt-spray environments on an extruded AZ31magnesium alloy OriginalResearch Article[J]. Corrosion Science, Volume56, March2012, Pages194-208.
[65]Lokesh Choudhary, R.K. Singh Raman. Effect of yttrium, calcium and zirconiumon ignition-proof principle and mechanical properties of magnesium alloysOriginal Research Article[J]. Journal of Rare Earths, Volume30, Issue1, January2012, Pages74-78.
[66]XM Chen,GY Li,JS Lian,Q Jiang. An organic chromium-free conversion coatingon AZ91D magnesium alloy. App Surf Sci,2008,255:2322-2328.
[67]XJ Cui, CH Liu, RS Yang, XZ Lin, MG. Recent progress in corrosion protectionof magnesium alloys by organic coatings Review Article[J]. Progress in OrganicCoatings, Volume73, Issues2–3, February–March2012, Pages129-141.
[68]陈拂晓，郭俊卿，孙付涛.AZ31B镁合金热压缩变形的组织变化与变形机制[J].塑性工程学报.2012，12(5):78-84.
[69]SX Zhang,XN Zhang,CL Zhao,et al. Research on an Mg-Zn alloy as a degradablebiomaterial. Acta Biomaterialia,2010,6:626-640.
[70]XY Lu, Yu Zuo, XH Zhao, YM Tang. Comparative studies on as-castmicrostructures and mechanical properties between Mg3Ce1.2Mn0.9Sc andMg3Ce1.2Mn1Zn magnesium alloys Original Research Article[J]. Transactions ofNonferrous Metals Society of China, Volume22, Issue1, January2012, Pages53-59.
[71]孙秋霞材料腐蚀与防护[M]冶金工业出版社2007.
[2] XN Gu, W Zheng, Y Cheng, YF Zheng. A study on alkaline heattreated Mg–Caalloy for the control of the biocorrosion rate. Acta Biomaterialia,2009,5:2790-2799.
[3]RZ Zhu. Corrosion of Metal [J]. Beijing: Metallurgical Industry Press,1993
[4]D L Albright. In: Paris H G, Hunt W H eds., Advances in Magnesium Alloys andComposites, Phoenix, Arizona: Internatioal Magnesium Association and theNon-ferrous Metals Committee, TMS,1988:48.
[5] X L Wu. Institute of Corrosion and Protection of Metals [J]. The ChineseAcademy of Science,1999.
[6]李高林，文九巴，贺俊光等.稀土Y对AZ80镁合金组织及耐蚀性能的影响[J].材料热处理学报.2012,(2):20-25.
[7].WQ Zhou, DY Shan, EH Han, et al. Structure and formation mechanism ofphosphate conversion coating on die-cast AZ91D magnesium alloy [J]. CorrosSci,2008,50(2):319-327.
[8]牛丽媛.镁合金锌系复合磷化膜成膜机理-微观结构及性能的研究[D].长春：吉林大学，2006.
[9]Kuwahara H, Al-Abdullat Y, Mazaki N, et al, Precipitation of magnesium apatiteon pure magnesium surface during immersing in Hank’s solution. Mater Trans,2001,42:1317-1321.
[10]金华兰，危仁杰，杨湘杰.镁合金磷酸盐转化膜层生长过程及其腐蚀率[J].特种铸造及有色合金，2005，25(11)：651-653.
[11]Dyugulu O, Kaya RA, Oktay G, et al. Investigation on the potential of magnesiumalloy AZ31as a bone implant. Mater Sci Forum,2007,421:546549.
[12]金华兰. ZM5镁合金磷酸盐表面改性处理技术[R].南昌：南昌大学，2005，7.
[13]David, Hawke, and D.L. Al bright. A phosphate permanganate conversion coatingfor magnesium[J].Metal Finishing,1995,10:34-38.
[14]曹洪志，邹振宇，陈波等.过共晶铝硅镁合金的研究现状及发展趋势[C].2012(第22届)重庆市铸造年会论文集.重庆大学材料科学与工程学院.国家镁合金材料工程技术研究中心.
[15] GY Li, JS Lian, LY Niu, et al. Growth of zinc phosphate coatings on AZ91Dmagnesium alloy, Surf Coat Technol,2006,201:1814-1820.
[16] D L Albright. Relationship of microstructures and corrosion behavior inmagnesium alloy ingots and castings [J]. Advances in magnesium alloys andcomposites,1988,8:60.
[17]M. Khosro Aghayani, B. Niroum. Effects of ultrasonic treatment onmicrostructure and tensile strength of AZ91magnesium alloy Original ResearchArticle[J]. Journal of Alloys and Compounds, Volume509, Issue1,5January2011, Pages114-122.
[18]徐开东.镁合金高能表面强化研究[D]武汉：华中科技大学，2010.
[19]Mohammad Reza Elahi, Mahmoud Heydarzadeh Sohi. Grain growth kinetics ofbulk AZ31magnesium alloy by hot pressing Original Research Article[J]. Journalof Alloys and Compounds, Volume527,25June2012, Pages193-196.
[20]刘燕，卢国龙，刘金丹，李亮.AZ91D镁合金表面电沉积n-ZrO_2/Ni复合镀层及耐蚀性研究[J].功能材料.2012,2(24):45-49.
[21]沟引宁，李鑫洋.表面活性剂对镁合金浸锌的影响[J].表面技术.2012，2(11):55-60.
[22] GY Li, JS Lian, LY Niu, et al. Growth of zinc phosphate coatings on AZ91Dmagnesium alloy [J]. Surf&Coatings Technol,2006,201(3/4):1814-1820.
[23]Cheng Zhong, Fan Liu, Yating Wu, Jingjing Le, Lei Liu, Meifeng He, Jiacai Zhu,Wenbin Hu. Liquid phase surface alloying of AZ91D magnesium alloy with Aland Ni powders Original Research Article[J]. Journal of Alloys and Compounds,Volume520,15April2012, Pages11-21.
[24] LY Niu, ZH Jiang, GY Li, et al. A study and application of zinc phosphatecoating on AZ91D magnesium alloy, Surf Coat Technology,2006,200:3021-3026.
[25]陈福文，余琨，陈良建等.Mg-6%Zn-10%(β-Ca3(PO4)2复合材料的制备及腐蚀降解行为[J].中国有色金属学报.2012，11(52):120-125.
[26] Unigovski Y B, Gutman E M. Surface Morphology of a Diecast Mg Alloy[J].Applied Surface Science,1999,153(1):47-52.
[27]宋诗哲.腐蚀电化学研究方法[M].北京：化学工业出版社，1988.
[28]徐淑强AZ91D镁合金环保型磷化膜制备技术、微观结构及其耐腐蚀性能研究[D]重庆：西南大学，2009.
[29]李新凯，张治民，赵亚丽.变形镁合金的研究现状及前景[J].热加工工艺.2011，25(53):142-146.
[30] XM Chen, GY Li, JS Lian, et al. Study of the formation and growth of tannicacid based conversion coating on AZ91D magnesium alloy. Surf Coat Technol,2009,204:736-747.
[31]钟丽应.稀土元素对AZ91镁合金组织结构和腐蚀行为的影响[J].浙江大学,2008.
[32]王芬.AZ31镁合金表面有机膜的耐蚀性能[J].特种铸造机有色合金.2011.35(24)：1104-1109
[33]HoungYuHsiao，Wen TaTsai.CharaeteriZationofanodiefilmsfor medon AZ9LdMagnesium alloy [J].Surface&Coatings Technology，2005，190:299-308.
[34] CL Wen,S K Guan,L Peng, et al. Characterization and degradation behavior ofAZ31alloy surface modified by bone-like hydroxyapatite for implant applications.App Surf Sci,2009,255:6433-6438.
[35]姜鹏. AZ91D镁合金表面化学转化及溶胶—凝胶技术制备复合涂层研究[J].哈尔滨哈尔滨工程大学,2007.
[36]崔作兴，顾云飞，邵忠才等.镁合金化学转化膜的制备及其性能研究[J].分子科学学报.2012,2(26):50-55.
[37]LP Xu, PC Feng, GN Yu, L Yang, et al. In vitro and in vivo evaluation of thesurface bioactivity of a calcium phosphate coated magnesium alloy[J].Biomaterials,2009,30:1512-1523.
[38]A. Dhanapal, S. Rajendra Boopathy, V. Balasubramanian. The Influence ofMechanical Surface Treatments on Fatigue Behavior of Extruded AZ61Magnesium Alloy Original Research Article[J]. Materials Science andEngineering: A, In Press, Accepted Manuscript, Available online12April2012
[39]游丽英.镁合金表面锌系磷化膜制备工艺及性能研究[D]长春：吉林大学，2007
[40]蒋晓军，陈昌国，刘瑜萍等.稀土强化镁合金耐蚀性能的研究进展[J].腐蚀与防护.2012,10(14):88-92.
[41]T.S. Srivatsan, C. Godbole, M. Paramsothy, M. Gupta. Hydrogen sorptionkinetics of magnesium hydride enhanced by the addition of Zr8Ni21alloyOriginal Research Article[J]. Journal of Alloys and Compounds, In Press,Accepted Manuscript, Available online30March2012.
[42]刘正.镁合金压铸及其铸件低周疲劳行为与裂纹扩展的研究[D].沈阳:中国科学院金属研究所，2001，15-17.
[43]CH Ye, YF Zheng, SQ Wang, TF Xi, YD Li. Low Cycle Fatigue Behavior ofAZ91D Magnesium Alloy Containing Rare-Earth Ce Element Original ResearchArticle[J]. Procedia Engineering, Volume27,2012, Pages1794-1800.
[44]赵磊，钟辉，龚国辉.镁合金的激光表面处理技术[J].轻合金加工技术.2012,6(41):90-95.
[45]YB Ren,H Wang,JJ Huang, et al, Study of biodegradation of pure magnesium.Key Eng Mater,2007,342.343:601-604.
[46]李光玉.镁合金表面有机涂层和化学镀层的研究[D]长春：吉林大学，2006.
[47]S.A. Pighin, G. Capurso, S. Lo Russo, H.A. Peretti. The Improved Performanceof a Mg-Rich Epoxy Coating on AZ91D Magnesium Alloy by Silane PretreatmentOriginal Research Article[J]. Corrosion Science, In Press, Accepted Manuscript,Available online3April2012.
[48]王晓明，查吉利，陈敏强等.压铸高危镁合金废料回收技术与设备研发[J].特种铸造及有色合金.2011，35(24)：1114-1119.
[49]X Wang, LX Hu, K Liu, YL Zhang.Influence of pH value, chloride ionconcentration and immersion time on corrosion rate of friction stir welded AZ61Amagnesium alloy weldments Review Article[J]. Journal of Alloys and Compounds,Volume523,15May2012, Pages49-60.
[50]雷作鍼，胡梦珍编译.金属的磷化处理[M].北京：机械工业出版社，1992
[51]尚伟，温玉清，李秀广等.AZ91D镁合金微弧氧化电参数对其耐蚀性的影响[J].表面技术.2012(2):10-14
[52]Md. Shahnewaz Bhuiyan, Yoshiharu Mutoh, A.J. McEvily. The role of aluminumoxide particulate reinforcements on cyclic fatigue and final fracture behavior of anovel magnesium alloy Original Research Article[J]. Materials Science andEngineering: A, Volume532,15January2012, Pages196-211.
[53]牛丽媛.镁合金锌系复合磷化膜成膜机理微观结构及性能的研究[D].长春：吉林大学，2006.
[54]陶军，龙思远，刘瑜等.镁合金有机涂层体系研究现状及发展趋势[J].热加工工艺.2011,25(53):133-137.
[55]S. Amira, J. Huot. Effect of cold rolling on hydrogen sorption properties ofdie-cast and as-cast magnesium alloys Original Research Article[J]. Journal ofAlloys and Compounds, Volume520,15April2012, Pages287-294.
[56]周婉秋，单大勇，曾荣昌等.镁合金的腐蚀行为与表面防护方法[J].材料
[57]]钱苗根姚寿山张少宗编著现代表面技术.[M].北京：机械工业出版社，2002
[58]周勇，熊金平，李依旋.PH和时间对镁合金表面磷化膜形貌和耐蚀性的影响[J].电镀与精饰.2012，7(4)：63-68.
[59]RG Hu, S Zhang, JF Bu, CJ Lin, GL Song. The Types and DistributionCharacterization of Al-Mn Phases in the AZ61Magnesium Alloy OriginalResearch Article[J]. Procedia Engineering, Volume27,2012, Pages833-839.
[60]A. Fabre, J.E. Masse. Magnesium alloys as body implants: Fracture mechanismunder dynamic and static loadings in a physiological environment OriginalResearch Article[J]. Acta Biomaterialia, Volume8, Issue2, February2012, Pages916-923.
[61]JF FAN,ZY CHEN, WD YANG, S FANG, BS XU. In vitro corrosion andbiocompatibility study of phytic acid modified WE43magnesium alloy OriginalResearch Article[J]. Applied Surface Science, Volume258, Issue8,1February2012, Pages3420-3427.
[62]Christopher A. Walton, Holly J. Martin, M.F. Horstemeyer, Paul T. Wang.Preparation and Characterization of Phosphate Film for Magnesium Alloy AZ31Original Research Article[J]. Physics Procedia, Volume25,2012, Pages194-199.
[63]刘瑜，龙思远，张小红，曾聪.AZ61镁合金的差热分析及凝固组织观察[C].2012(第22届)重庆市铸造年会论文集.重庆大学材料科学与工程学院.国家镁合金材料工程技术研究中心.
[64]MB YANG, FS PAN. Quantification of corrosion mechanisms under immersionand salt-spray environments on an extruded AZ31magnesium alloy OriginalResearch Article[J]. Corrosion Science, Volume56, March2012, Pages194-208.
[65]Lokesh Choudhary, R.K. Singh Raman. Effect of yttrium, calcium and zirconiumon ignition-proof principle and mechanical properties of magnesium alloysOriginal Research Article[J]. Journal of Rare Earths, Volume30, Issue1, January2012, Pages74-78.
[66]XM Chen,GY Li,JS Lian,Q Jiang. An organic chromium-free conversion coatingon AZ91D magnesium alloy. App Surf Sci,2008,255:2322-2328.
[67]XJ Cui, CH Liu, RS Yang, XZ Lin, MG. Recent progress in corrosion protectionof magnesium alloys by organic coatings Review Article[J]. Progress in OrganicCoatings, Volume73, Issues2–3, February–March2012, Pages129-141.
[68]陈拂晓，郭俊卿，孙付涛.AZ31B镁合金热压缩变形的组织变化与变形机制[J].塑性工程学报.2012，12(5):78-84.
[69]SX Zhang,XN Zhang,CL Zhao,et al. Research on an Mg-Zn alloy as a degradablebiomaterial. Acta Biomaterialia,2010,6:626-640.
[70]XY Lu, Yu Zuo, XH Zhao, YM Tang. Comparative studies on as-castmicrostructures and mechanical properties between Mg3Ce1.2Mn0.9Sc andMg3Ce1.2Mn1Zn magnesium alloys Original Research Article[J]. Transactions ofNonferrous Metals Society of China, Volume22, Issue1, January2012, Pages53-59.
[71]孙秋霞材料腐蚀与防护[M]冶金工业出版社2007.