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材料研究学报  2018, Vol. 32 Issue (4): 301-308    DOI: 10.11901/1005.3093.2017.192
  研究论文 本期目录 | 过刊浏览 |
阳极氧化电解质的组分对钛基体和表面涂层的影响
王倩, 何代华(), 刘平, 刘新宽, 马凤仓, 李伟, 陈小红, 张珂
上海理工大学材料科学与工程学院 上海 200093
Effect of Anodizing Electrolyte Formula on Quality of Oxidizing Film on Ti6Al4V
Qian WANG, Daihua HE(), Ping LIU, Xinkuan LIU, Fengcang MA, Wei LI, Xiaohong CHEN, Ke ZHANG
School of Materials Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093, China
引用本文:

王倩, 何代华, 刘平, 刘新宽, 马凤仓, 李伟, 陈小红, 张珂. 阳极氧化电解质的组分对钛基体和表面涂层的影响[J]. 材料研究学报, 2018, 32(4): 301-308.
Qian WANG, Daihua HE, Ping LIU, Xinkuan LIU, Fengcang MA, Wei LI, Xiaohong CHEN, Ke ZHANG. Effect of Anodizing Electrolyte Formula on Quality of Oxidizing Film on Ti6Al4V[J]. Chinese Journal of Materials Research, 2018, 32(4): 301-308.

全文: PDF(5977 KB)   HTML
摘要: 

在浓度为0.15 mol/L的HF电解液中加入浓度为5 g/L的磷酸二氢钙(Ca(H2PO4)2)进行阳极氧化,研究了Ca和P对阳极氧化后钛合金表面的物相组成和形貌的影响;进而用水热电化学方法在Ti6Al4V基体表面进行阴极沉积,研究了Ca、P元素对羟基磷灰石(HA)涂层物相、形貌、涂层结合强度的影响。进行细胞的粘附实验,测试了涂层的生物活性。结果表明:含有磷酸二氢钙的电解液阳极氧化后TiO2纳米管的管径比未加磷酸二氢钙的管径大,表面的Ca、P含量提高,且Ca的含量明显变化。用水热电化学沉积生成的HA涂层表现为分层生长模式,下层为致密均匀的棒状,上层则为丰富度更大的团絮状。涂层与基体的结合强度由18.93 MPa提高到23.74 MPa。在粘附实验过程中细胞更易于依附团絮状HA涂层生长,加入磷酸二氢钙后团絮状羟基磷灰石增多,增大了细胞的依附生长空间,为细胞提供更大的生长接触面积,有利于植入体与人体结合。

关键词 无机非金属材料Ca(H2PO4)2阳极氧化水热电化学细胞粘附实验    
Abstract

The anodizing film on Ti6Al4V was prepared via anodic oxidizing in electrolyte of 0.5 mol/L hydrofluoric acid with different addition amount of 5 g/L Ca(H2PO4)2. Then the effect of Ca and P on the phase composition, surface morphology and adhesive strength of the anodizing film was investigated. Hydroxyapatite coatings were deposited on the Ti6Al4V with oxidizing film by hydrothermal-electrochemical method and then of which the biological activity was examined by cell adhesion experiment. Results show that the diameter of TiO2- tubes of the anodizing film prepared in the bath with Ca(H2PO4)2 was lager than that without Ca(H2PO4)2, and the Ca- and P-content for the former film increased, especially Ca. HA coatings presented layered structure, of which the much compact inner portion composed of rod-like grains and the top portion presented flocculent oxidizing film. The adhesive strength between the coating and the substrate increases from 18.93 MPa to 23.74 MPa. During the cell adhesion experiment, it was easily for cells to attached on the flocculent surface of HA coatings, which can supply bigger space for cells to live, therewith, increasing the combination of implants and the human body.

Key wordsinorganic non-metallic materials    Ca(H2PO4)2    anodic oxidation    hydrothermal-electrochemical    cell adhesion experiment
收稿日期: 2017-04-17     
基金资助:资助项目 中国科学院特种无机涂层重点实验室开放课题项目(KLICM-2014-11)和上海市自然科学基金(15ZR1428300)
作者简介:

作者简介 王 倩,女,1986年生,硕士生

图1  在不同电解液中Ti6Al4V阳极氧化后的XRD图谱
图2  Ti6Al4V在不同电解液中阳极氧化后的SEM照片
图3  在HF电解液中阳极氧化后试样的能谱
图4  在HF-Ca(H2PO4)2电解液中阳极氧化后试样的能谱
图5  Ti6Al4V在不同电解液中阳极氧化后水热电化学沉积HA的XRD图谱
图6  Ti6Al4V在不同电解液中阳极氧化后水热电化学沉积HA涂层的SEM照片
图7  不同电解液下试样的拉伸断面SEM照片
图8  在不同条件下试样表面细胞的增殖数据
图9  细胞在羟基磷灰石涂层上的粘附
[1] Paulina Str?kowska, René Beutner, Marcin Gnyba.Electrochemically assisted deposition of hydroxyapatite on Ti6Al4Vsubstrates covered by CVD diamond films—Coating characterization and first cell biological results[J]. Mater. Sci. Eng. C, 2016, 59: 624
[2] R.E, Neuendorf, E. Saiz, A.P. Tomsia, et al. Adhesion between biodegradable polymers and hydroxyapatite: Relevance to synthetic bone-like materials and tissue engineering scaffolds[J]. Acta. Biomater., 2008, 4(5): 1288
[3] Sun X, Yang X Y, Su Y, et al.Morphology Improvement of Sandblasted and Acid-Etched Titanium Surface and Osteoblast Attachment Promotion by Hydroxyapatite Coating[J]. Rare. Metal. Mat. Eng., 2015, 44(1): 0067
[4] Gu J B, Li H, Yang H X, et al.The Development of Microstructure Formation in Plasma Sprayed Hydroxyapatite Coatings[J]. Therm. Spray Technol., 2014, 6(1): 10(谷佳宾, 李辉, 杨海鑫等. 等离子喷涂羟基磷灰石涂层微观组织形成的研究现状[J]. 热喷涂技术, 2014, 6(1): 10)
[5] Shi H Y, Hu R, Lin C J.A study on controllable preparation of nanohydroxyapatite coatings on Ti substrate by electrochemical deposition[J]. J. Funct. Mater., 2006, 37(1): 98(时海燕, 胡仁, 林昌健. 电沉积法可制备纳米羟基磷灰石涂层的研究, 功能材料[J]. 功能材料, 2006, 37(1): 98)
[6] P. Layrolle, C. Van der valk, R. Dalmeijer, Biomimetic calcium phosphate coatings and their biological performances [J]. Key Eng. Mater., 2001,192-195: 391
[7] E. Antonov, V. Bagratashvili, M. Ball, Influence of target density on properties of laser deposited calcium phosphate coatings [J]. Key Eng. Mater., 2001, 192-195: 107
[8] GAO Y L, Xiong D S.Study on plasma sprayed hydroxyapatite coating on magnesium alloy[J]. Transactions of Materials and Heat Treatment, 2011, 32(1): 109(高亚丽, 熊党生. 医用镁合金等离子喷涂羟基磷灰石涂层研究[J]. 材料热处理学报, 2011, 32(1): 109)
[9] Han J Y, Yu Z T, Zhou L.Effects of composite TiO2 on the crystal of hydroxyapatite prepared by sol- gel method[J]. Heat Treat. Met., 2008, 33(7): 12(韩建业, 于振涛, 周廉. TiO2对溶胶凝胶法制备羟基磷灰石晶化的影响[J]. 金属热处理, 2008, 33(7): 12)
[10] N. Eliaz, M. Eliyahu.Electrochemical processes of nucleation and growth of hydroxyapatite on titanium supported by real-time electrochemical atomic force microscopy[J]. J. Biomed. Mater. Res., Part A, 2007, 80A(3): 621
[11] F. Ma, P. Liu, W. Li, et al.Hydroxyapatite growth on Ti MAO surface assisted by the addition of calcium and phosphate ions in hydrothermal treatment solution[J]. Rare. Metal. Mat. Eng., 2012,41: 478
[12] Zhang L Y, Gao Y, Liu Z X, et al.Preparation and Characterization of N-Doped TiO2 Nanotube[J]. Rare. Metal., 2011, 35(4): 504(张理元, 曹阳, 刘钟馨等. 氮掺杂二氧化钛纳米管的制备及表征[J]. 稀有金属, 2011, 35(4): 504)
[13] Wang Q, Wang W, Cui F Y, et al.Preparation modification and application of titanium dioxide nanotubes[J]. Chem. Ind. Eng. Prog., 2015, 34(5): 1311(王俏, 王威, 崔福义等. 二氧化钛纳米管的制备、改性及应用, 化工进展[J]. 2015, 34(5): 1311)
[14] B. Yang, M. Uchida, H. Kim, et al.Preparation of bioactive titanium metal via anodic oxidation treatment[J]. Biomaterials, 2004, 25(6): 1003
[15] Wang P.Influence of anodic oxidation pretreatment on Ti6Al4V alloy and the HA coating deposited by hydrothermal- electrochemical methods [D]. Master Thesis, University of Shanghai for Science and Technology, 2015(王朴. 阳极氧化处理钛合金对水热电化学沉积HA涂层的影响, 硕士学位论文, 上海理工大学, 2015)
[16] Qiao L P, Jiang L F, Huang H D, et al.Effects of calcium salts and KOH concentrations on surface morphology and chemical compositions of micro arc oxidation coatings on titanium alloys[J]. Chin. J. Nonferrous Met., 2015, 25(6): 1590(乔丽萍, 江龙发, 黄华德等. 钙盐和氢氧化钾浓度对钛合金微弧氧化表面形貌及成分的影响[J]. 中国有色金属学报, 2015, 25(6): 1590)
[17] Yang X C, Cui X l, Ren P, et al. Influence of post-treatment process on the bioactivity of anodized titanium[J]. J. Funct. Mater.,2015, 46(1):01135(杨修春, 崔晓琳, 任鹏等. 后处理工艺对阳极氧化钛生物活性的影响[J]. 功能材料, 2015, 46(1): 01135)
[18] Gong X.Preparation and biological assessment of strontium- subtituted nanohydroxyapatite coating on sandblasted-dual acid etched titanium surface [D]. Master Thesis, Zhejiang University School of Medicine, 2012(龚雪. 多孔纯钛表面纳米掺锶羟基磷灰石涂层构建及其生物学评价 [D]. 硕士学位论文, 浙江大学, 2012)
[19] Liang J H, Xiao X F, Liu R F, et al.Fabrication and Thermal Stability of TiO2 Nanotube Arrays by Anodic Oxidation at Wide Range of Voltage[J]. Chin. J. Inorg. Chem., 2010, 26(1): 112(梁建鹤, 肖秀峰, 刘榕芳等. 宽电压范围下阳极氧化制备TiO2纳米管阵列及其热稳定性[J]. 无机化学学报, 2010, 26(1): 112)
[20] Katarzyna Suchanek, Amanda Bartkowiak, Agnieszka Gdowik, et al.Crystalline hydroxyapatite coatings synthesized under hydrothermal conditions on modified titanium substrates[J]. Mater. Sci. Eng. C, 2015, 51: 57
[21] D W Gong, Craig A, Grimes, et al. Titanium oxide nanotube arrays prepared by anodic oxidation[J]. J. Mater. Res., 2001, 16(12): 3331
[22] Li W P, Shi P, Preparation and Its Forming Mechanism of Micron-Dimensional Porous TiO2 Films on the Surface of Pure Titanium[J]. Rare. Metal. Mat. Eng., 2008, 37(12): 2253(李维平, 石萍. 纯钛表面微米级多孔TiO2薄膜的制备及形成机制[J]. 稀有金属材料与工程, 2008, 37(12): 2253)
[23] Tao H J, Tao J, Wang L, et al.Fabrication of nano-porous TiO2 films on pure titanium and its alloy[J]. Journal of Nanjing University of Aeronautics & Astronautics, 2005, 37(5): 597(陶海军, 陶杰, 王玲. 纯钛及其合金表面纳米多孔TiO2膜的制备研究[J]. 南京航空航天大学学报, 2005, 37(5): 597)
[24] Shirkhanzadeh M, Direct formation of nanophase hydroxyapatite on cathodically polarized electrodes[J]. J. Mater. Sci., 1998, (2): 67
[25] Ban S, Maruno S, Harada A, et al.Effect of temperature on morphology of electrochemically-deposited calcium phosphates[J]. Dent. Mater. J.,1996, 15(1): 31
[26] Du J, He D H, Liu P, et al.Hydroxyapatite Coatings on Titanium Substrate Prepared by Hydrothermal-Electrochemical Deposition[J]. Chin. J. Mater. Res., 2016, 30(10):787
[27] Yan X K, Bioseparation Engineering [M]. Beijing, Chemical Industry Press, 2001
[28] J WANG, Y G CHAO, Q B WAN, Fluoridated hydroxyapatite coatings on titanium obtained by electrochemical deposition[J]. Acta. Biomater., 2009, 5(5): 1798
[29] Park H H, Park I S, Kim K S, et al.Bioactive and electrochemical charaterization of TiO2 nanotubes on titanium via anodic oxidation[J]. Electrochimica. Acta., 2010, 55(20): 6109
[30] Fu T, Li H, Zhang Y M, et al.Effect of Current Density Changes on the Properties of Hydroxyapatite Biocoatings[J]. Rare. Metal. Mat. Eng., 2000, 29(4):247(付涛, 李浩, 张玉梅等. 电流密度对电结晶羟基磷灰石生物涂层性能的影响[J]. 稀有金属材料与工程, 2000, 29(4): 247)
[31] R ZHANG, Y WAN, X AI, et al.Preparation of micro-nanostructure on titanium implants and its bioactivity[J]. Nonferrous. Met. Soc. China, 2016, 26(4): 1019
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