医用钛表面生物活性化研究

钛及钛合金具有优良的生物相容性和机械性能,已应用于临床,尤其是用作骨替换与修复材料.但是,钛属于生物惰性材料,不能与骨组织形成化学键合或称骨键合.通过表面改性可使其在生理环境具有诱导羟基磷灰石在表面自发生长的能力,即生物活性化.这是当今生物医用材料研究的热点领域之一.本文评述了钛表面生物活化的研究现状,简要总结了本课题组在这方面的研究工作.     

钛基生物复合材料的研究进展

钛及钛合金由于具有优秀的抗腐蚀性、生物相容性、低密度和高的比强度等特性,而被应用于生物医学方面。然而,与人骨相比,钛合金的弹性模量较高,可达100～110GPa,而人骨的弹性模量只有10～30 GPa。虽然与其它金属材料相比具有与骨较为接近的弹性模量,但仍远远高于骨的弹性模量,这就容易造成钛与人体骨界面上力学性能的不匹配,如直接植入则会带来“应力屏蔽“效应,因此对钛及钛合金进行处理来降低弹性模量和提高活性成为当前研究的热点。目前主要通过两种途径来改善纯钛及其合金的生物活性和生物相容性问题,一种就是通过各种不同工艺在纯钛及其合金表面涂覆羟基磷灰石及生物玻璃涂层,另一种是将生物活性材料HA作为一种活性相混入纯钛及其合金中,形成一种微观复合材料。本文重点介绍了近年来钛基生物复合材料的研究进展。     

生物医用多孔钛的表面仿生处理研究进展

介绍了钛作为生物医用材料的研究现状.针对多孔钛的结构特点,综述了当前生物医用材料的各种表面活化方法,如溶胶-凝胶法、预钙化处理法、碱热处理法、酸碱两步法等,总结了当前多孔钛表面改性和骨诱导机理的研究现状.     

生物医用多孔钛及钛合金的研究进展

多孔钛和钛合金因具有优异的生物相容性、与人骨力学性能匹配良好、可作为植入物材料的优点,而引起了广泛关注。介绍了医用多孔钛及钛合金的产生背景,综述了近几年国内外对生物医用多孔钛及钛合金的制备方法、微结构特征与性能的关系、表面处理的研究进展,并展望了生物医用多孔材料的发展。     

新型生物活性材料的设计和研究进展

生物活性材料是生物医用材料领域中一个重要的研究方向.研究表明,在体液的作用下这类材料的表面能够形成Si-OH、Ti-OH、Ta-OH、-COOH和PO4H2等功能基团,从而诱导类骨磷灰石层生成并与骨发生键合.综述了人们利用医用金属进行表面生物活化或通过有机/无机复合的方法得到力学性能良好的新型生物活性材料,为人工植入体的临床应用提供了更广阔的前景.     

骨修复用生物玻璃复合材料研究进展

生物玻璃是一类性能优良的生物材料,具有良好的生物活性和生物相容性,作为骨修复植入体可以在材料界面与人体骨组织之间形成化学键合,诱导骨的修复与再生.将生物玻璃与其它材料进行复合,可以制备出生物活性和机械性能优良的骨修复复合材料.综述了生物玻璃复合材料的研究现状,并探讨了该类材料目前存在的不足,展望了其发展趋势.     

医用金属表面含锶涂层耐蚀性和生物相容性研究进展

随着全球人口老龄化进展以及骨关节疾病发病率的增加,人们对于骨修复医用金属材料的需求日益增多.生物医用金属材料包括不可降解钛及可降解金属镁和铁.金属材料在耐蚀性及骨整合方面存在一些不足,有必要对其表面改性进一步优化.锶元素具有促进成骨抑制破骨的作用,将其用作改性成分对提高医用金属表面骨细胞活性具有重要意义.本文主要对近年来医用金属钛、镁和铁表面掺锶涂层在耐蚀性和生物相容性方面进行了归纳及比较.重点介绍了锶与降解性、生物相容性好的载体(如羟基磷灰石、透钙磷石等)结合制备的复合涂层在钛合金、镁合金表面及铁合金表面提高骨整合性能的研究.最后,提出将锶元素与锌元素结合使得金属材料在促进骨修复的同时具有抗菌性能的建议.     

医用钛合金骨移植材料的研究现状

纯钛及钛合金以其优异的生物相容性、抗腐蚀性及与骨相近的弹性模量,在医学领域中获得了越来越广泛的应用.综述了医用钛合金骨移植材料的发展现状,并从抗磨损、耐腐蚀及生物活性3方面阐述了钛及其合金的表面改性技术.     

微弧氧化和碱处理对钛的细胞粘附和骨植入行为的影响研究

考察了微弧氧化处理和碱处理对钛表面形貌、涂层成分、羟基磷灰石沉积能力、细胞黏附、骨内植入的影响。结果表明,微弧氧化和碱复合处理后的钛表面TiO2薄膜呈现大量裂缝,表现出表面含大量OH-极性基团的纳米多孔网状结构,此微观结构和组成使材料诱导羟基磷灰石生成能力显著,利于成骨细胞黏附及繁殖,无细胞毒性,细胞兼容性好。通过植入兔股骨4和12周体内动物实验组织学切片表明,材料无毒、无刺激性,与周围组织间有良好的组织相容性,该材料植入动物骨环境中可刺激成骨,具有骨传导作用。相比下,微弧氧化和碱复合处理样品的生物相容性较为优异。     

钛氧膜生物相容性与生物活性的研究与应用

对钛氧膜的生物相容性和生物活性的研究及应用进行了评述.重点讨论了钛氧膜的制备方法、钛氧膜的活化处理方式以及钛氧膜在心血管材料和骨替代材料中的应用前景.     

Characterization of surface oxide films on titanium and bioactivity

Biological properties of titanium implant depend on its surface oxide film. In the present study, the surface oxide films on titanium were characterized and the relationship between the characterization and bioactivity of titanium was studied. The surface oxide films on titanium were obtained by heat-treatment in different oxidation atmospheres, such as air, oxygen and water vapor. The bioactivity of heat-treated titanium plates was investigated by immersion test in a supersaturated calcium phosphate solution. The surface roughness, energy morphology, chemical composition and crystal structure were used to characterize the titanium surfaces. The characterization was performed using profilometer, scanning electronic microscopy, ssesile drop method, X-ray photoelectron spectroscopy, common Bragg X-ray diffraction and sample tilting X-ray diffraction. Percentage of surface hydroxyl groups was determined by X-ray photoelectron spectroscopy analysis for titanium plates and density of surface hydroxyl groups was measured by chemical method for titanium powders. The results indicated that heat-treatment uniformly roughened the titanium surface and increased surface energy. After heat-treatment the surface titanium oxide was predominantly rutile TiO₂, and crystal planes in the rutile films preferentially orientated in (1 1 0) plane with the highest density of titanium ions. Heat-treatment increased the amount of surface hydroxyl groups on titanium. The different oxidation atmospheres resulted in different percentages of oxygen species in TiO₂, in physisorbed water and acidic hydroxyl groups, and in basic hydroxyl groups on the titanium surfaces. The immersion test in the supersaturated calcium phosphate solution showed that apatite spontaneously formed on to the rutile films. This revealed that rutile could be bioactivated. The analyses for the apatite coatings confirmed that the surface characterization of titanium has strong effect on bioactivity of titanium. The bioactivity of the rutile films on titanium was related not only to their surface basic hydroxyl groups, but also to acidic hydroxyl groups, and surface energy. Heat-treatment endowed titanium with bioactivity by increasing the amount of surface hydroxyl groups on titanium and its surface energy.     

Hydrogen distribution in titanium materials with low outgassing property

This paper addresses a hydrogen outgassing mechanism in titanium materials with extremely low outgassing property by investigating hydrogen atoms distribution in depth around the surface in a titanium material and stainless steel. The evacuation time dependence of depth profiles of positive hydrogen ions was measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS). In the stainless steel, concentration of hydrogen atoms decreases slowly at the surface oxide layer, while it decreases rapidly in the bulk by vacuum evacuation. Thus, the surface oxide layer is considered to prevent hydrogen diffusions in the bulk. On the other hand, in the titanium material, hydrogen atoms show maximum concentration at the boundary between the surface oxide layer and the bulk titanium. Moreover, concentration of hydrogen atoms decreases rapidly at the surface oxide layer, while those decrease slowly in the deep region below the surface-bulk boundary by vacuum evacuation. It is suggested that the boundary between the surface oxide layer and bulk titanium plays a role of a barrier for bulk hydrogen diffusions. These facts give very low hydrogen concentration near the surface, which results in an extremely low outgassing rate in titanium materials.     

Influence of nanostructure on titanium corrosion resistance in fluoridated medium

ABSTRACT

Nanocrystalline titanium, mainly owing to its high corrosion resistance, mechanical strength to density ratio and biocompatibility, has a great application potential in dental implantology. However, fluoridated agents commonly used for oral hygiene could have a destructive influence on the titanium protective passive films and lead to the formation of local corrosion damages. In this work, the effect of nanostructuring on titanium corrosion resistance in the concentration of F^? which is typical for toothpastes, was evaluated by different electrochemical and surface characterisation techniques. It was found that nanostructure influences beneficially on titanium corrosion resistance in fluoride solution. Furthermore, the lower increase in nanocrystalline titanium surface roughness in corrosion solutions indicates better stability of passive film formed on its surface.

This paper is part of a thematic issue on Titanium.     

Bioactive TiOB‐Coating on Titanium Alloy Implants Enhances Osseointegration in a Rat Model

The surface properties of titanium alloy implants for improved osseointegration in orthopaedic and dental surgery have been modified by many technologies. Hydroxyapatite coatings with a facultative integration of growth factors deposited by plasma spraying showed improved osseointegration. Our approach in order to enhance osseointegration was carried out by a surface modification method of titanium alloy implants called plasma chemical oxidation (PCO). PCO is an electrochemical procedure that converts the nm‐thin natural occurring titanium‐oxide layer on an implant to a 5 µm thick ceramic coating (TiOB‐surface). Bioactive TiOB‐surfaces have a porous microstructure and were loaded with calcium and phosphorous, while bioinert TiOB‐surfaces with less calcium and phosphorous loadings are smooth. A rat tibial model with bilateral placement of titanium alloy implants was employed to analyze the bone response to TiOB‐surfaces in vivo. 64 rats were randomly assigned to four groups of implants: (i) pure titanium alloy (control), ii) titanium alloy, type III anodization, (iii) bioinert TiOB‐surface, and (iv) bioactive TiOB‐surface. Mechanical fixation was evaluated by pull out tests at 3 and 8 weeks. The bioactive TiOB‐surface showed significantly increased shear strength at 8 weeks compared to all other groups.     

Influence of hierarchical hybrid micro/nano-structured surface on biological performance of titanium coating

In this article, hierarchical hybrid micro/nano-structured titanium surface was obtained by alkali treating the vacuum plasma sprayed titanium coating following hot water immersing for 24 h. The influences of the surface microstructure on the in vitro and in vivo biologic performance of titanium coating were studied. Human bone marrow-derived stromal cells (hBMSCs) were used for in vitro cytocompatibility evaluation. Compared with the rough titanium coating surface, cell behaviors, such as spread and proliferation were apparently enhanced by mimicking the hierarchical hybrid structure of bone tissue, while ALP expression was lower at days 4 and 7. With the expanding of induction time, the ALP activity rapidly increased on the hierarchical surface. After 10 days induction, it became much higher than that on the rough titanium surface. A canine model was applied for an in vivo evaluation of the bone bonding ability. Histologic examination demonstrated that new bone was formed more rapidly on the hierarchical surface implants than that on the rough titanium surface. All these results indicate that the hierarchical surface is favorable for the response of hBMSCs and early bone bonding.     

Hydrogen content in titanium and a titanium–zirconium alloy after acid etching

Dental implant alloys made from titanium and zirconium are known for their high mechanical strength, fracture toughness and corrosion resistance in comparison with commercially pure titanium. The aim of the study was to investigate possible differences in the surface chemistry and/or surface topography of titanium and titanium–zirconium surfaces after sand blasting and acid etching. The two surfaces were compared by X-ray photoelectron spectroscopy, secondary ion mass spectroscopy, scanning electron microscopy and profilometry.The 1.9 times greater surface hydrogen concentration of titanium zirconium compared to titanium was found to be the major difference between the two materials. Zirconium appeared to enhance hydride formation on titanium alloys when etched in acid. Surface topography revealed significant differences on the micro and nanoscale. Surface roughness was increased significantly (p < 0.01) on the titanium–zirconium alloy. High-resolution images showed nanostructures only present on titanium zirconium.     

汽车用钛合金表面双辉等离子Mo合金化层的制备及其摩擦磨损性能

为了改善钛合金的表面摩擦磨损性能,采用双辉等离子合金化法在汽车用近β型钛合金(Ti-5Zn-3Sn)表面制备了Mo合金层,通过微观组织观察及硬度、摩擦系数、磨损率测试等考察了合金化层的形貌以及摩擦磨损性能.结果表明:钛合金表面等离子合金化后,呈现出银白色,表面形貌很不平整,粗糙度和致密性得到提高.钛合金Mo合金化层与基体之间结合很好,没有出现不可控的断层以及裂纹.随着合金化层的逐渐深入,Mo元素占比慢慢降低.在Mo元素固溶强化作用的影响之下,钛合金表面硬度得到明显提高,有效地改善了钛合金表面摩擦学性能.随着Mo合金化温度增加,合金化层的硬度明显增加.合金化后钛合金表面硬度高,受压屈服极限大,黏着效应小,摩擦系数小,磨损率明显降低.     

钛表面固定纤维连接蛋白及其体外细胞培养

通过低温等离子聚合的方法,以丙烯酸为单体在钛表面沉积含有羧基的薄膜,以羧基为接入点固定纤维连接蛋白。样品表面用X射线光电子能谱、傅里叶红外光谱仪进行表征。将固定了纤维连接蛋白的样品进行体外细胞培养,所用的细胞为MG63骨瘤细胞,对照样为纯钛。结果表明, 钛表面聚丙烯酸薄膜能有效地固定纤维连接蛋白,并且固定纤维连接蛋白的样品能促进骨瘤细胞的生长和黏附,具有更高的成骨活性。      

Electrodeposition of amine-terminatedpoly(ethylene glycol) to titanium surface

The immobilization of poly(ethylene glycol), PEG, to a solid surface is useful to functionalize the surface, e.g., to prevent the adsorption of proteins. No successful one-stage technique for the immobilization of PEG to base metals has ever been developed. In this study, PEG in which both terminals or one terminal had been modified with amine bases was immobilized onto a titanium surface using electrodeposition. PEG was dissolved in a NaCl solution, and electrodeposition was carried out at 310 K with − 5 V for 300 min. The thickness of the deposited PEG layer was evaluated using ellipsometry, and the bonding manner of PEG to the titanium surface was characterized using X-ray photoelectron spectroscopy after electrodeposition. The results indicated that a certain amount of PEG was adsorbed on titanium through both electrodeposition and immersion when PEG was terminated by amine. However, terminated amines existed at the surface of titanium and were combined with titanium oxide as N–HO by electrodeposition, while amines randomly existed in the molecule and showed an ionic bond with titanium oxide by immersion. The electrodeposition of PEG was effective for the inhibition of albumin adsorption. This process is useful for materials that have electroconductivity and a complex morphology.     

Amount of hydroxyl radical on calcium-ion-implanted titanium and point of zero charge of constituent oxide of the surface-modified layer

To compare the surface properties of calcium-ion (Ca2+)-implanted titanium with those of titanium and to investigate the mechanism of bone conductivity of Ca2+-implanted titanium, amounts of hydroxyl radical of Ca2+-implanted titanium and titanium were estimated. Also, the point of zero charge (p.z.c.) of oxide constituting surface oxides of Ca2+-implanted titanium and titanium was determined. Results showed that the amount of active hydroxyl radical on Ca2+-implanted titanium was found to be significantly larger than that on titanium, indicating that the number of electric-charging sites of Ca2+-implanted titanium in electrolyte is more than that of titanium. The p.z.c. values of rutile (TiO2), anatase (TiO2), and perovskite (CaTiO3), were estimated to be 4.6, 5.9, and 8.1, respectively. Thus, Ca2+-implanted titanium surface is charged more positively in bioliquid than titanium, accelerating the adsorption of phosphate ions. © 1998 Chapman & Hall