纳米钛基TiO_2薄膜生长特点和生物活性研究

采用直流磁控溅射法分别在纳米晶体钛和粗晶粒工业纯钛表面沉积TiO2薄膜,研究了纳米钛基TiO2薄膜的结构形貌、形核、生长、晶体结构和体外生物活性。用扫描电镜和X射线衍射仪分析了薄膜的表面形貌和晶体结构,用体外模拟人体体液浸泡诱导羟基磷灰石生长实验表征薄膜的生物活性。结果表明:纳米钛基薄膜形核率高,薄膜非常致密、光滑,晶粒细小,仅为粗晶粒钛基TiO2薄膜晶粒尺寸的一半,约100nm;钛基材纳米晶体化可促进薄膜由锐钛矿相向金红石相转变;钛基材纳米化可显著提高自身及其表面TiO2薄膜的生物活性。     

TiO2纳米管阵列的热稳定性及生物活性的研究

通过电化学阳极氧化法,在纯钛片表面制备得到TiO2纳米管阵列.研究了TiO2纳米管阵列的热稳定性,并通过模拟体液浸泡研究了其生物活性.采用扫描电镜(SEM)和X射线衍射(XRD)分别对纳米管阵列的形貌和物相进行表征.结果表明,当热处理温度为300℃时,TiO2纳米管由无定形向锐钛型转变,温度升到500℃时转变为金红石型,升到600℃时TiO2纳米管阵列出现坍塌,700℃热处理时其形貌完全被破坏.生物活性研究表明,具有TiO2纳米管阵列的钛片经氢氧化钠溶液活化后具有良好的生物活性,能在模拟体液中诱导生成磷灰石.     

后处理工艺对阳极氧化钛生物活性的影响

钛及钛合金由于具有良好的力学、生物学性能,已成为良好的骨修复和替换材料。为了改善钛的生物活性,首先采用两步电化学阳极氧化法对金属纯钛进行表面改性,即使之表面形成多孔纳米结构,然后对样品进行不同的后处理,如450℃热处理,NaOH处理,NaOH-CaCl2处理,最后将后处理样品浸泡在人体模拟液(SBF)中,研究磷灰石在样品表面的生长情况。采用X射线衍射(XRD)、带能量散射谱(EDS)的场发射扫描电子显微镜(FE-SEM)、傅里叶变换红外光谱(FT-IR)、电感耦合等离子体发射光谱仪(ICP-OES)等对生成的磷灰石的物相、形貌、元素组成等进行表征。结果表明,非晶TiO2纳米管阵列不能诱导磷灰石在其表面生成,而经450℃退火处理后形成的结晶良好的锐钛矿相TiO2纳米管阵列具有一定生物活性,即可诱导部分磷灰石颗粒在其表面生成。进一步经NaOH-CaCl2溶液后处理可加速羟基磷灰石在样品表面的形成速度,样品在模拟体液(SBF)中浸泡8d后,表面生成的磷灰石厚度约为5μm,磷灰石层是由大量球形颗粒堆积而成的,而球形颗粒是由无数纳米薄片组成的花状结构。     

溶胶-凝胶法在多孔钛表面制备二氧化钛生物涂层

室温下利用溶胶-凝胶法在多孔钛表面制备TiO2薄膜,并分别于不同温度热处理.利用电化学工作站测试不同温度煅烧后的TiO2薄膜在0.9%NaCl生理盐水中的耐腐蚀特性;利用XRD、SEM测试技术研究样品在模拟体液(SBF)内浸泡不同时间后的生物活性和显微结构.结果表明,600℃退火的TiO2薄膜的生物活性最强,只在SBF中浸泡10天就形成表面致密的磷灰石涂层,并且涂层的结晶细小而薄,没有破坏多孔钛的孔隙结构;800℃退火的TiO2薄膜因其最为致密,在生理盐水中的耐腐蚀性最好.     

纳米晶体钛基掺钽TiO2薄膜的摩擦磨损性能

采用室温直流反应磁控溅射技术在纳米晶体钛表面制备掺钽TiO2薄膜,研究了掺Ta量对纳米晶体钛基TiO2薄膜摩擦磨损性能的影响。结果表明：在室温模拟人体体液条件下,掺钽TiO2薄膜与不锈钢淬火钢球（Φ4mm）对摩的磨损率为10^-6-10^-5mm^3·m^-1 N^-1级;随着Ta含量的增加,薄膜的摩擦系数和磨损率呈先...     

酸碱辅以热处理对钛表面生物活性的影响

利用先酸后碱复合处理钛表面,部分样品加热到450和700℃进行热处理,在钛表面获得不同形貌和不同晶型的TiO2薄膜。将样品浸泡于模拟体液中,观察表面HA沉积情况,并进行体外细胞毒性实验以探讨样品的生物相容性。结果表明,酸碱复合处理样品在450℃热处理后表现出最好的生物活性,主要归因于钛表面纳米级花蕊网状结构形貌。酸碱复合处理样品在700℃热处理后表现出最差的生物活性,这是因为此法处理后的样品表面呈现纳米棒晶体结构,纳米棒直径和长度均大于450℃热处理的纳米丝形貌的钛及未热处理钛,而且纳米棒紧密结合程度也高于450℃热处理及未热处理的钛,正是由于这样紧密的较大尺寸晶体结构造成其生物活性低于450℃热处理及未热处理的钛的情况。     

纳米结构316L不锈钢基掺钽TiO_2薄膜生物活性研究

采用射频磁控溅射技术在表面微结构纳米化316L不锈钢和粗晶粒316L不锈钢基体上制备掺钽TiO2薄膜。采用扫描电镜和X射线衍射仪分析薄膜形貌和晶体结构,用体外模拟人体体液浸泡实验研究薄膜的生物活性。结果表明:表面微结构纳米化的316L不锈钢具有强烈诱导掺钽TiO2薄膜形核效应;316L不锈钢表面微结构纳米化能显著提高自身及其表层掺钽TiO2薄膜的生物活性;316L不锈钢表面纳米化后,其表层掺钽TiO2薄膜诱导的羟基磷灰石形貌由原先的球状变为多孔网状结构。     

掺钽TiO2薄膜的生物活性研究

采用射频磁控溅射技术在表面纳米化316L不锈钢基体上制备掺钽TiO2薄膜,研究了不同掺钽量对表面纳米化316L不锈钢基TiO2薄膜形貌、结构、亲水性和生物活性的影响规律。结果表明掺杂适量的钽能够细化TiO2薄膜颗粒;掺钽能够改善TiO2薄膜的亲水性和生物活性;含钽36%的TiO2薄膜表面自由能比未掺杂时提高了30.1mN/m,在SBF溶液中能促进羟基磷灰石在其表面晶化。     

离子束合成TiO2薄膜对医用NiTi合金表面的改性

采用离子束增强沉积法制备TiO2薄膜,对医用NiTi合金进行表面改性处理。系统研究了薄膜的表面组成、结构、形貌及耐蚀性、亲水性等与血液相容性相关的表面性质。NiTi合金表面沉积TiO2薄膜后,抗模拟体液的腐蚀性提高,凝血时间延长。为进一步提高TiO2薄膜的抗凝血性,对TiO2薄膜的进一步表面改性－表面结合肝素分子进行了初步尝试,结果表明,薄膜表面组成发生变化,表面亲水性进一步提高。     

纯钛表面立方介孔SiO2薄膜诱导沉积碳磷灰石层

采用浸渍-提拉法在预处理纯钛表面制备立方介孔SiO₂薄膜, 通过评价体外诱导类骨碳磷灰石层形成能力研究其生物活性。利用小角X射线衍射、傅立叶变换红外光谱、N₂吸附、电镜和能谱等测试技术对模板剂去除前后、模拟体液浸泡前后介孔薄膜结构、组成与形貌进行了研究; 利用固体表面Zeta电位仪研究薄膜表面荷电性质。结果表明, 介孔薄膜具有三维立方介孔结构, 在模拟体液(1.5SBF)中浸泡14 d即能诱导碳磷灰石层在其表面沉积, 显示出良好的生物活性。介孔薄膜独特的孔道结构以及孔表面Si-OH在体液中呈负电性对其生物活性起关键作用。     

Effects of oxygen content on bioactivity of titanium oxide films fabricated on titanium by electron beam evaporation

The titanium oxide films were fabricated on titanium metal by e-beam deposition technique in various oxygen partial pressures in order to investigate the effects of oxygen content in titanium oxide film on the bioactivity of titanium implant. The nano-sized titanium oxide particles were observed on the surface of specimens. Raman spectra showed that titanium oxide films deposited by e-beam evaporator had oxygen deficient TiO2 structure. The oxygen content in oxide films was calculated from the high resolution XPS spectra of Ti 2p. The densities of HA particles formed on the sample surfaces after immersion test in SBF became higher as the contents of oxygen in titanium oxide films increased. We concluded that the degree of hydroxyl group formation in SBF depended on the stoichiometry of TiO2, which enhanced the bioactivity of titanium.     

Surface modification of cp-Ti using femtosecond laser micromachining and the deposition of Ca/P layer

Femtosecond laser processing is employed to create regular patterns and bioactive layer on the surface of pure titanium. Surface morphology and microstructure of the laser-processed layer are characterized by scanning electron microscope (SEM) and transmission electron microscope (TEM). The results show that the processing with varied laser energies builds a surface with three-order roughness from nanometer scale to micrometer scale. Selected area electron diffraction indicates that some kind of TiO layer emerges on the surface after femtosecond laser machining. The bioactivity of TiO layer is further evaluated by soaking it in simulated body fluid (SBF). SEM observation and EDX analysis show that Ca/P layer is rapidly formed on the surface of TiO layer after SBF soaking. It implies that TiO layer with unique three-order roughness has good bioactivity.     

Influence of calcinated and non calcinated nanobioglass particles on hardness and bioactivity of sol�Cgel-derived TiO2�CSiO2 nano composite coatings on stainless steel substrates

Thick films of calcinated and non calcinated nanobioglass (NBG)-titania composite coatings were prepared on stainless steel substrates by alkoxide sol-gel process. Dip-coating method was used for the films preparation. The morphology, structure and composition of the nano composite films were evaluated using environmental scanning electron microscope, X-ray diffraction and Fourier transform infrared spectroscope. The SEM investigation results showed that prepared thick NBG-titania films are smooth and free of macrocracking, fracture or flaking. The grain size of these films was uniform and nano scale (50-60 nm) which confirmed with TEM. Also FTIR confirmed the presence of Si-O-Si bands on the calcinated NBG-titania films. The hardness of the prepared films (TiO(2)-calcinated NBG and TiO(2)-Non calcinated NBG) was compared by using micro hardness test method. The results verified that the presence of calcinated NBG particles in NBG-titania composite enhanced gradually the mechanical data of the prepared films. The in vitro bioactivity of these films was discussed based on the analysis of the variations of Ca and P concentrations in the simulated body fluid (SBF) and their surface morphologies against immersion time. Surface morphology and Si-O-Si bands were found to be of great importance with respect to the bioactivity of the studied films. The results showed that calcinated NBG-titania films have better bioactivity than non calcinated NBG-titania films.     

Characterization of Sol-gel-derived TiO2 and TiO2-SiO2 Films for Biomedical Applications

In order to improve the corrosion resistance and biocompatibility of NiTi surgical alloy, TiO2 and TiO2-SiO2 thin films were prepared by sol-gel method. The surface characteristics of the film, which include surface composition, microstructure and surface morphology, were studied by X-ray diffraction (XRD), atomic force microscopy (AFM) and X-ray photoelectron spectra (XPS), respectively. A scratching test was used to assess the interface adhesive strength between the film and substrate. The corrosion resistance of NiTi alloy coated with oxide films were studied by anodic polarization curves measurement in biological solution. Additionally, a preliminary study of the in vitro bioactivity of the films was conducted. The results indicated that TiO2 and TiO2-SiO2 (Ti/Si=4:1) films have higher electrochemical corrosion resistance and can be used as protective layers on NiTi alloy. In addition, TiO2-SiO2 composite films have better bioactivity than TiO2 film.     

Formation and bioactivity of porous and nanostructured TiO2/beta-TCP coating on titanium

Titanium and its alloys have been widely used as hard tissue implants due to their excellent mechanical properties and biocompatibility. However, their near bio-inertness and metallic ion release are still the problems with clinical uses. In this paper, porous and nanostructured TiO2/beta-tricalcium phosphate (beta-TCP) composite coatings were prepared on titanium substrates by plasma electrolytic oxidation (PEO) in a Ca and P-containing electrolyte. The influence of PEO electric current density on phase composition and bioactivity of the coatings were studied. X-ray diffraction, scanning electron microscopy and Fourier transfer infrared spectroscopy were utilized to characterize the phase composition and microstructure of the coatings. Simulated body fluid immersion tests were employed on the coatings to evaluate their bioactivity. The results reveal that TiO2/beta-TCP composite coating with pores size less than 10 microm and grains of 50-100 nm in size was prepared. The electric current density of PEO is an important factor in the formation of the composite coating. The TiO2/beta-TCP composite coating shows good bioactivity, which are attributed to the incorporation of beta-TCP.     

酸-水热法辅以水热温度对钛材生物活性的影响

为提高医用钛材的生物活性,通过酸-水热复合法在其表面设计并制备了TiO_2纳米棒,探讨水热温度对钛表面TiO_2纳米棒形成的影响,然后对试样进行模拟体液生物活性实验,采用扫描电子显微镜(SEM)、能谱仪(EDS)和X射线衍射仪(XRD)分析手段研究了钛表面生成产物的形貌、元素组成和物相组成.结果表明:随着水热温度的增加,二氧化钛层的表面形貌发生改变,从片状到棒状,之后纳米棒发生团聚;试样中金红石相和锐钛矿相的衍射峰强度随水热温度的增加而增强;水热温度为130℃时,钛表面可以形成尺寸均匀、长度基本一致的TiO_2纳米棒,其厚度、长度和直径分别为2.5μm、150 nm和10 nm,且纳米棒是由锐钛矿型和金红石型TiO_2的混合相组成.模拟体液生物活性实验后,水热处理后材料表面有富含Ca、P的羟基磷灰石生成,而羟基磷灰石的形成主要与纳米棒的形成和膜层的厚度有关.其中,水热温度为130℃时形成的纳米棒结构较好,膜层较厚,其表面诱导磷灰石沉积的含量最多,具有较好的生物活性.     

The effect of sodium-ion implantation on the properties of titanium

This paper deals with the surface modification of titanium by sodium-ion implantation and with the effect of this modification on structure, corrosion resistance, bioactivity and cytocompatibility. The Na ions were implanted with doses of 1 x 10(17) and 4 x 10(17) ions/cm(2) at an energy of 25 keV. The chemical composition of the surface layers formed during the implantation was examined by secondary-ion mass spectrometry (SIMS) and X-ray photoelectron spectroscopy (XPS), and their microstructure--by transmission electron microscopy (TEM). The corrosion resistance was determined by electrochemical methods in a simulated body fluid (SBF) at a temperature of 37 degrees C, after exposure in SBF for various times. The surfaces of the samples were examined by optical microscopy, by scanning electron microscopy (SEM-EDS), and by atomic force microscopy (AFM). Biocompatibility of the modified surface was evaluated in vitro in a culture of the MG-63 cell line and human osteoblast cells. The TEM results indicate that the surface layers formed during the implantation of Na-ions are amorphous. The results of the electrochemical examinations obtained for the Na-implanted titanium samples indicate that the implantation increases corrosion resistance. Sodium-ion implantation improves bioactivity and does not reduce biocompatibility.     

Deposition of Bioactive Layer on NiTi Alloy by Chemical Treatment

A simple chemical method was developed for inducing bioactivity on NiTi alloys(50 at.pct by Ni/Ti).A layer of calcium phosphate was deposited on the surface to improve biocompatibility of thealloy.NiTi alloys were first etched in HNO3 aqueous solution,and then treated with boiling diluted NaOH solution.A rough surface was created and a thin TiO2 layer was formed on the surface.Pre-calcification was then introduced by immersing the treated NiTi alloys in supersaturated Na2HPO4 solution and supersaturated Ca(OH)2 solution in turn before calcification in simulated body fluid (SBF).A dense and uniform bonelike calcium phosphate(Ca-P) bioactive layer was formed on the surfaces of the specimen,which would improve their biocompatibility.Morphology and element analysis on NiTi surfaces during the treatments were investigated in detail by means of environment scanning electron microscopy(ESEM),energy dispersion X-ray spectroscopy(EDXS),and X-ray diffraction (XPD).