钛表面涂覆类金刚石碳膜的生物相容性研究

将涂覆金刚石碳（ＤＬＣ）膜的金属钛植入狗的下颌骨，用Ｘ射线，光镜，透射电镜（ＴＥＭ）和扫描电镜（ＳＥＭ）等手段观测新骨细胞形貌，数量，琥珀酸脱氢酶（ＳＤＨ）的活性以及种植体表面的骨结合情况。结果表明，用直流辉光放电法制备的ＤＬＣ涂膜明显改善钛植入体的生物相容性。     

纯钛经电化学表面改性后的抗菌活性与生物相容性研究

在含不同电解质的电解液中利用电化学方法对纯钛进行表面改性,并将改性后的纯钛试样进行抗菌性和生物相容性实验.结果表明,纯钛在含氯化物的电解液中经表面改性后具有良好的抗茵活性和生物相容性,而在非氯化物的电解液中经表面改性后其抗茵活性和生物相容性则较差.     

非晶碳膜的表面润湿性对生物相容性的影响

采用等离子体注入沉积方法(PⅢ-D),混合通入C2H2、Ar或N2,制备了具有不同表面润湿性的非晶碳薄膜a-CH和掺N非晶碳薄膜a-CNH.采用Raman及XPS方法对薄膜的结构进行了分析,采用血小板黏附实验评价薄膜的抗凝血性能,采用材料表面的内皮细胞培养,对材料的细胞毒性以及生物相容性进行评价.结果表明非晶碳膜的生物相容性的提高与其表面的润湿性的变化密切相关,可通过掺杂特定的元素,增加a-CH薄膜表面张力的极性倾向,提高非晶碳膜的亲水性,来进一步改进a-CH薄膜的生物相容性,特别是血液相容性.     

表面氧污染影响钛膜吸氢量的机理

表面氧污染的钛膜，其吸氢能力比清洁钛膜降低达数倍之多。在厚度ｄ＝４００Ａ，表面氧污染的钛膜上重新蒸镀，使其表面再生一层极薄的清洁钛膜。吸氢，释氢测量表明其吸氢能力得到恢复。     

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。     

表面氧污染影响钛膜吸氢量的机理

表面氧污染的钛膜，其吸氢能力比清洁钛膜降低达数倍之多，在厚度ｄ为４０ｎｍ，表面氧污染的钛膜表面上，重新蒸镀一层极薄的（约１．２ｎｍ）清洁钛膜，吸氢，释氢的测量表明其吸氢能力得到恢复。另外，还对其他四块不同厚度的钛膜，在表面清洁及氧污染的条件下，分别进行了吸氢能力实验，实验结果证实，氧污染降低钛氢能力的原因是使钛膜土氢分子解离的位置减少，而不是扩散阻挡层的作用。     

壳聚糖复合不对称膜的制备及生物组织相容性研究

用分步流延干燥法制备了一种由壳聚糖（CS）、聚乙烯醇（PVA）、羧甲基壳聚糖（CM-CS）构成的新型人工皮肤医用材料——壳聚糖复合不对称膜（C-P-C膜），其上层为CS层，中间为PVA层，下层为CM-CS层。研究结果表明，可通过调节CS、PVA、CM-CS的加入量来控制复合不对称膜各层的厚度和膜的水蒸气通透性，C-P-C膜具有良好的透光性和吸水率。生物相容性实验发现，C-P-C膜是无毒材料，不会引起创伤感染，随着植入C-P-C膜时间的延长，组织炎症反应明显减轻，6周时，炎症浸润程度低于手术缝合线。C-P-C膜能够明显地促进创面愈合，能有效地密封出血创面且具有显著的止血作用。     

表面氧污染影响钛膜吸氢量的机理

表面氧污染的钛膜，其吸氢能力比清洁钛膜降低达数倍之多。在厚度d为40nm，表面氧污染的钛膜表面上，重新蒸镀一层极薄的（约1．2nm）清洁钛膜，吸氢、释氢的测量表明其吸氢能力得到恢复。另外，还对其他四块不同厚度的钛膜，在表面清洁及氧污染的条件下，分别进行了吸氢能力实验。实验结果证实：氧污染降低钛膜吸氢能力的原因是使钛膜上氢分子解离的位置减少，而不是扩散阻挡层的作用。     

生物电子学领域中的生物材料与生物相容性研究

生物电子学是一门涉及生物学、电子学、化学、物理、材料及信息技术等许多学科的交叉学科,生物电子学发展中的一些科学问题直接与生物材料及其生物相容性研究有关。从生物电子学的概念出发,从微电子植入器件、植入器件相关电极制造技术及表面改性、体外神经芯片表面修饰与改性3个方面,结合本实验室的相关研究工作,讨论了生物电子学领域中的生物材料与生物相容性研究进展,指出了生物材料和生物电子学的交叉是未来科学发展的必然趋势。     

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.     

微图形氧化钛薄膜表面内皮细胞生长行为研究

采用非平衡磁控溅射沉积技术制备微图形化的Ti-O薄膜,通过在微图形化的薄膜表面培养内皮细胞的方法,研究了微图形及表面物理化学性能对细胞生长行为的影响.结果表明,微图形尺寸减小到某一尺度范围之内会对内皮细胞在材料表面的生长起到接触引导作用,促进细胞在其表面生长;同时,表面成分、结构和表面能参数γsp/γsd也在一定程度上影响内皮细胞的生长行为.采用溅射技术使材料表面具有一定特征的表面微观形貌,能够引导和促进细胞在材料表面的生长,溅射技术制备微图形化表面可能成为等离子体生物材料表面改性的一个新的技术手段.     

Application-wise nanostructuring of anodic films on titanium: a review

The interest in titanium and its oxides keeps growing on account of their peculiar engineered properties, which find applications in several fields, from architecture to bioengineering, from automotive to photovoltaic cells and photocatalytic devices, as well as to produce self-cleaning surfaces. This review intends to provide an overview of anodic oxidation treatments currently applied to form nanostructured oxide layers on titanium, with special reference to their whole range of applications. The different procedures and parameters of anodic oxidation will be described, giving information on the main oxide characteristics achievable: thickness, morphology, structure and composition. An analysis of the fields of application associated with specific oxide characteristics will be provided, in order to highlight the variety of properties that can be obtained, and the importance of tuning such properties as a function of the specific application.     

两种不同结构TiO2薄膜生物活化能力比较

采用非平衡磁控溅射法制备了2种不同结构的TiO2薄膜，对所得TiO2薄膜分别运用碱处理和酸处理2种化学方法进行表面处理，期望在材料表面获得羟基活性基团。运用X射线衍射（XRD）、X射线光电子能谱仪（XPS）等手段研究了薄膜的表面结构、成分等。利用傅立叶红外技术（FTIR）对活化处理前后样品表面的羟基基团进行检测，同时利用四探针测试仪对薄膜的电阻率进行了测量。结果表明，运用碱处理和酸处理2种方法，可以在锐钛矿型TiO2薄膜表面形成活性羟基基团；相比于金红石型TiO2薄膜，锐钛矿型具有较好的羟基活化能力。     

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.     

氧化钛薄膜表面等离子体处理引发官能团形成的研究

采用水/氧气,丙烯酸/氧气脉冲射频等离子体处理方法,对氧化钛薄膜进行表面改性.结果表明,水蒸气/氧气混合气体等离子体处理在氧化钛薄膜表面产生了吸附水及游离羟基,丙烯酸/氧气混合气体等离子体处理在氧化钛薄膜表面形成了羟基、羧基和羰基官能团.经水蒸气/氧气、丙烯酸/等离子体处理的氧化钛薄膜的水接触角分别降低了67.3和58.5°,极性分量分别增加了36.5和50.9mJ/m2,表现出很好的亲水性.     

Effect of nickel oxide seed layers on annealed-amorphous titanium oxide thin films prepared using plasma-enhanced chemical vapor deposition

The effect of a nickel oxide (NiO_x) seed layer on the crystallization and photocatalytic activity of the sequentially plasma-enhanced chemical vapor deposited amorphous titanium oxide (TiO_x) thin film processed by a post-annealing process was investigated. The evolution of the crystalline structures, chemical bond configurations, and surface/cross-sectional morphologies of the annealed TiO_x films, with and without a NiO_x seed layer, was examined using X-ray diffractometer, Fourier transform infrared spectrometry, X-ray photoelectron spectroscopy, atomic force microscopy, and field emission scanning electron microscope measurements. Thermo- and photo-induced hydrophilicity was determined by measuring the contact angle of water droplet. Photocatalytic activity after UV light irradiation was evaluated from the decolorization of a methylene blue solution. The crystallization temperature of the TiO_x film, deposited on a NiO_x seed layer, was found to be lower than that of a pure TiO_x film, further improving the thermo- and photo-induced surface super-hydrophilicity. The TiO_x film deposited onto the NiO_x seed layer, resulting in significant cluster boundaries, showed a rough surface morphology and proved to alleviate the anatase crystal growth by increasing the post-annealing temperature, which yielded a more active surface area and prohibited the recombination of photogenerated electrons and holes. The photocatalytic activity of the NiO_x/TiO_x system with such a textured surface therefore was enhanced and optimized through an adequate post-annealing process.     

Mechanical properties and scratch resistance of filtered-arc-deposited titanium oxide thin films on glass

The mechanical properties and the scratch resistance of titanium oxide (TiO₂) thin films on a glass substrate have been investigated. Three films, with crystalline (rutile and anatase) and amorphous structures, were deposited by the filtered cathodic vacuum arc deposition technique on glass, and characterized by means of nanoindentation and scratch tests. The different damage modes (arc-like, longitudinal and channel cracks in the crystalline films; Hertzian cracks in the amorphous film) were assessed by means of optical and focused ion beam microscopy. In all cases, the deposition of the TiO₂ film improved the contact-mechanical properties of uncoated glass. Crystalline films were found to possess a better combination of mechanical properties (i.e. elastic modulus up to 221 GPa, hardness up to 21 GPa, and fracture strength up to 3.6 GPa) than the amorphous film. However, under cyclic sliding contact above the critical fracture load, the amorphous film was found to withstand a higher number of cycles. The results are expected to provide useful insight for the design of optical coatings with improved contact-damage resistance.     

介孔TiO2的合成及表征

以氯化十六烷基吡啶(C16PyCl)为模板剂,在不同条件下合成了一系列介孔TiO2(m-TiO2),分别用红外光谱(FT-IR)、X射线粉末衍射(XRD)和BET比表面测定等技术对介孔TiO2的结构、晶相和比表面积进行了表征,探讨了模板剂、溶剂、溶液PH、老化温度和C16PyCl／TTIP摩尔比的影响。结果表明,在本实验条件下,最佳合成条件是C16PyCl为模板剂,溶剂为C2H5OH,PH=7～8,老化温度20℃,C16PyCl／TTIP摩尔比为2。     

多孔氧化钛储氢的研究

采用配体辅助模板法,以异丙醇钛为前体,使用不同碳链长度的烷基胺为模板剂来制备一系列不同比表面积和孔容的多孔氧化钛材料。采用X射线衍射,氮气吸附实验,透射电镜对所制取材料进行表征,并在77K的条件下测量所制取材料的储氢性能。结果表明,在材料中拥有最大比表面积的材料具有最高的储氢量,在77K和65大气压的条件下其重量和体积储氢量分别为3.92wt%和21.48kg/m3。     

Photocatalytic oxidation of nitric oxide with immobilized titanium dioxide films synthesized by hydrothermal method

Gas-phase photocatalytic oxidation (PCO) of nitric oxide (NO) with immobilized TiO2 films was studied in this paper. The immobilized TiO2 films were synthesized by hydrothermal method. The characterization for the physicochemical properties of catalysts prepared under different hydrothermal conditions were carried out by X-ray diffraction analysis (XRD), transmission electron microscopy (TEM), high resolution-transmission electron microscopy (HR-TEM), Brunauer-Emmett-Teller measurements (BET) and scanning electron micrograph (SEM). It was found that the PCO efficiency of the catalyst was mainly depended on the hydrothermal conditions. The optimal values of hydrothermal temperature and hydrothermal time were 200 degrees C and 24 h, respectively. Furthermore, it was also known that the photocatalytic efficiency would decrease remarkably when the calcination temperature was over than 450 degrees C. Under the optimal conditions (hydrothermal condition: 200 degrees C for 24 h; calcination temperature: 450 degrees C), the photocatalytic efficiency of catalyst could reach 60% higher than that of Degussa P25.