钛合金表面TiO_2薄膜制备及生物活性研究
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摘要
使用TiCl_3盐酸溶液作为前驱液,通过简单易操作的水热法在Ti-6Al-4V合金基体表面原位生长TiO_2纳米棒阵列薄膜。使用扫描电子显微镜(SEM)、场发射电子显微镜(FESEM)和X射线衍射仪(XRD)等手段研究不同水热反应条件对其表面形貌和结构的影响。结果表明:纳米棒阵列薄膜为混晶结构,具有沿[001]轴择优生长和金红石(101)高能晶面曝露的特点,并且能够适用于3D打印的多孔钛合金种植体,说明了该薄膜具有一定的普适性。该基体表面的TiO_2在3d就能诱导羟基磷灰石的生长,说明其具有优异的生物活性,显示了其在骨科、牙科等植入体表面改性领域的应用前景。
The titanium trichloride(TiCl_3)was used as the precursor,and titania nanorod films were highly ordered grew on Ti-6Al-4 Valloy substrate via a facile hydrothermal method.The morphology and crystal structure of titania film were characterized by scanning electron microscopy(SEM),field-emission electron microscope(FESEM)and X-ray diffraction(XRD).The results demonstrated that the as-deposited titania film was mischcrystal,with rutile highenergy(101)facet exposed.It was preferential grew along [001]orientation,which was perpendicular to the surface.Moreover,the hydrothermal method can also be adopted in 3D printing titanium alloy implant.The apatite would grow on the as-treated implant after immersion in simulated body fluid(SBF)for 3 days,which has good vitro bioactivity and great potential for application in surface modification of orthopedics and dental implants.
The titanium trichloride(TiCl_3)was used as the precursor,and titania nanorod films were highly ordered grew on Ti-6Al-4 Valloy substrate via a facile hydrothermal method.The morphology and crystal structure of titania film were characterized by scanning electron microscopy(SEM),field-emission electron microscope(FESEM)and X-ray diffraction(XRD).The results demonstrated that the as-deposited titania film was mischcrystal,with rutile highenergy(101)facet exposed.It was preferential grew along [001]orientation,which was perpendicular to the surface.Moreover,the hydrothermal method can also be adopted in 3D printing titanium alloy implant.The apatite would grow on the as-treated implant after immersion in simulated body fluid(SBF)for 3 days,which has good vitro bioactivity and great potential for application in surface modification of orthopedics and dental implants.
引文
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[2]LONG M,RACK H J.Titanium alloys in total joint replacement-a materials science perspective[J].Biomaterials,1998,19(18):1621-1639.
[3]GEETHA M,SINGH A K,ASOKAMANI R,et al.Ti based biomaterials,the ultimate choice for orthopaedic implants-A review[J].Progress in materials science,2009,54(3):397-425.
[4]XIAO F,JIANG G Q,CHEN J Y,et al.Apatite-forming ability of hydrothermally deposited rutile nano-structural arrays with exposed{101}facets on Ti foil[J].Journal of materials science,2018,53(1):285-294.
[5]肖帆,倪爱珍,柳星竹,等.钛基体表面纳米二氧化钛薄膜生长及控制[J].浙江工业大学学报,2015,43(3):301-310.
[6]YANG H G,SUN C H,QIAO S Z,et al.Anatase TiO2single crystals with a large percentage of reactive facets[J].Nature,2008,453(7195):638-641.
[7]DAI Y Q,COBLEY C M,ZENG J,et al.Synthesis of anatase TiO2 nanocrystals with exposed{001}facets[J].Nano letters,2009,9(6):2455-2459.
[8]LIU S W,YU J G,JARONIEC M.Tunable photocatalytic selectivity of hollow TiO2 microspheres composed of anatase polyhedra with exposed{001}facets[J].Journal of the American chemical society,2010,132(34):11914-11916.
[9]PAN J,LIU G,LU G M,et al.On the true photoreactivity order of{001},{010},and{101}facets of anatase Tio2crystals[J].Angewandte chemie-international edition,2011,50(9):2133-2137.
[10]HAN X G,KUANG Q,JIN M S,et al.Synthesis of titania nanosheets with a high percentage of exposed(001)facets and related photocatalytic properties[J].Journal of the American chemical society,2009,131(9):3152-3153.
[11]LI T Y,TIAN B Z,ZHANG J L,et al.Facile tailoring of anatase TiO2morphology by use of H2O2:from microflowers with dominant{101}facets to microspheres with exposed{001}facets[J].Industrial&engineering chemistry research,2013,52(20):6704-6712.
[12]童少平,沈佟栋,倪金雷,等.金红石TiO2催化臭氧化磺基水杨酸[J].浙江工业大学学报,2015,43(6):591-594.
[13]傅凯杰.具有药物携带功能的多孔种植体及SLM制备[D].杭州:浙江工业大学,2016.
[14]HOSONO E,FUJIHARA S,KAKIUCHI K,et al.Growth of submicrometer-scale rectangular parallelepiped rutile TiO2films in aqueous TiCl3solutions under hydrothermal conditions[J].Journal of the American chemical society,2004,126(25):7790-7791.
[15]LIU Y,WANG H,WANG Y C,et al.Substrate-free,large-scale,free-standing and two-side oriented single crystal TiO2nanorod array films with photocatalytic properties[J].Chemical communications,2011,47(13):3790-3792.
[16]MORGAN B J,WATSON G W.A density functional theory plus U study of oxygen vacancy formation at the(110),(100),(101),and(001)surfaces of rutile TiO2[J].Journal of physical chemistry C,2009,113(17):7322-7328.
[17]HU W B,LI L P,TONG W M,et al.Supersaturated spontaneous nucleation to TiO2 microspheres:synthesis and giant dielectric performance[J].Chemical communications,2010,46(18):3113-3115.
[18]XIAO F,TSURU K,HAYAKAWA S,et al.In vitro apatite deposition on titania film derived from chemical treatment of Ti substrates with an oxysulfate solution containing hydrogen peroxide at low temperature[J].Thin solid films,2003,441(1/2):271-276.
[19]肖帆,柳星竹,江光强,等.钛表面原位自组装TiO2空心球及生物活性研究[J].浙江工业大学学报,2016,44(5):580-583.
[20]HANAWA T,Evaluation techniques of metallic biomaterials in vitro[J].Science and technology of advanced materials,2002,3(4):289-295.
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