非晶金刚石膜在口腔医学材料中的应用

采用带过滤的阴极真空等离子电弧镀膜技术,对口腔牙用聚甲基丙烯酸甲酯(PMMA)树脂及纯钛材料进行了表面镀覆非晶金刚石膜的改性处理,获得了镀覆非晶金刚石膜的PMMA树脂和镀覆非晶金刚石膜的纯钛口腔牙用材料。通过细胞培养和动物实验,考察了非晶金刚石膜的生物相容性。采用HA-1型涂层附着力划痕试验仪研究了非晶金刚石膜与PMMA树脂和与纯钛的结合力及镀覆非晶金刚石膜PMMA树脂和镀覆非晶金刚石膜纯钛的耐磨性能。在人工唾液中模拟口腔环境进行电化学分析测试了镀覆非晶金刚石膜纯钛材料的耐腐蚀性能。借助SEM观察了镀覆非晶金刚石膜纯钛材料的表面形貌。实验结果显示:非晶金刚石膜细胞毒性评级为0级,溶血率为3.08%,短期全身毒性试验为阴性;PMMA树脂经极化预处理后可镀覆结合力为(10.86±0.79)N的非晶金刚石膜;镀覆非晶金刚石膜纯钛表面自腐蚀电位和过钝化电位正移。表明非晶金刚石膜作为生物材料,其生物安全性、耐腐蚀性及镀膜结合强度达到口腔医用材料的要求。     

钛膜吸氢与释氢特性的研究

在SKL－12型多功能谱仪的预处理室中，采用超高真空镀膜的方法，得到了表面清洁的钛膜。对表面清洁及有一定量氧污染的钛膜进行了吸氢、释氢实验，并用理论模型拟合实验数据。结果表明：表面氧污染使钛膜吸氢能力降低，其原因在于氧原子占据了钛膜表面的吸附位置，使氢解离为原子的几率降低。     

高分子富氧膜材料的应用与发展

本文介绍了高分子富氧膜材料的富氧原理、影响其性能的因素及多种高分子富氧膜材料。并着重评述了这些材料在各领域的应用和研究、开发前景。     

废水处理中膜生物反应器的研究进展

膜生物反应器作为一种新型高效的生物处理技术和绿色技术,在水处理领域中得到了广泛的应用.综述了膜生物反应器在全世界的研究现状,膜生物反应器的构型、好氧膜生物反应器和厌氧膜生物反应器及应用情况,膜污染控制技术.探讨和展望了膜生物反应器的应用前景,指出了今后的研究方向.     

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。     

钛膜吸氢与释氢特性的研究

在ＳＫＬ－１２型多功能谱仪的预处理室中，采用超高真空镀膜的方法，得到了表面清洁的钛膜。对表面清洁及表面一定量氧污染的钛膜进行了吸氢，释氢实验，并用理论模型拟合实验数据。结果表明：表面氧污染使钛膜吸氢能力降低，其原因在于氧原子占据了钛膜表面的吸附位置，使Ｈ２解离为原子的几率降低。     

致密透氧膜的研究进展

介绍了混合导体致密透氧膜透氧机理，讨论了目前研究开发的钙钛矿型和类钙钛矿型透氧膜材料的性能。指出透氧膜材料的高温稳定性，高氧通量是需要解决的主要问题；提出了透氧膜反应器的应用及存在问题，并就致密透氧膜材料的应用前景进行了探讨。     

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。     

钛膜吸氢与释氢特性的研究

在ＳＫＬ－１２型多功能谱仪的预处理室中，采用超高真空镀膜的方法，得到了表面清洁的钛膜。对表面清洁及有一定量氧污染的钛膜进行了吸氢、释氢实验，并用理论模型拟合实验数据。结果表明：表面氧污染使太膜吸氢能力降低，其原因在于氧原子占据了钛膜表面的吸附位置，使氢解离为原子的几率降低。     

电化学及热处理氧化对商业纯钛耐蚀性能的影响

利用电化学氧化、热处理氧化对商业纯钛进行表面处理.不同的氧化电压和时间将产生不同形貌的氧化钛膜,电压过大时会生成很多的瘤状氧化物.热处理氧化后,钛表面生成均匀金红石和锐钛矿型混合氧化物膜,并且氧化膜下会出现Ti-O固溶体构成的渗氧层.在酸性含氯溶液和碱溶液中比较不同处理后钛板的腐蚀性能,在2种腐蚀介质中所有材料均随电位升高进入钝化区.在酸性溶液中,电化学氧化处理后钛板的腐蚀电流、维钝电流密度最小;在碱性溶液中,虽然热处理氧化对应维钝电流密度最小,但其钝化电位区间比电化学氧化对应电位区间窄.扫描电镜分析表明,热处理氧化膜随电位升高局部出现破损,而未经过表面处理的钛板,局部区域发生沿晶腐蚀.     

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.     

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.     

Influence of microstructure and chemical composition of sputter deposited TiO<Subscript>2</Subscript> thin films on in vitro bioactivity

Functionalisation of biomedical implants via surface modifications for tailored tissue response is a growing field of research. Crystalline TiO₂ has been proven to be a bone bioactive, non-resorbable material. In contact with body fluids a hydroxyapaptite (HA) layer forms on its surface facilitating the bone contact. Thus, the path of improving biomedical implants via deposition of crystalline TiO₂ on the surface is interesting to follow. In this study we have evaluated the influence of microstructure and chemical composition of sputter deposited titanium oxide thin films on the in vitro bioactivity. We find that both substrate bias, topography and the flow ratio of the gases used during sputtering affect the HA layer formed on the films after immersion in simulated body fluid at 37°C. A random distribution of anatase and rutile crystals, formed at negative substrate bias and low Ar to O₂ gas flow ratios, are shown to favor the growth of flat HA crystal structures whereas higher flow ratios and positive substrate bias induced growth of more spherical HA structures. These findings should provide valuable information when optimizing the bioactivity of titanium oxide coatings as well as for tailoring process parameters for sputtered-based production of bioactive titanium oxide implant surfaces.     

Ti-O/Ti-N复合薄膜的离子束合成及人工心脏瓣膜材料表面改性研究

采用离子束增强沉积（ＩＢＥＤ）等方法在热解碳、钛及钴合金等人工心脏瓣膜材料表面制备Ｔｉ－Ｏ、Ｔｉ－Ｎ及其复合薄膜。对薄膜的成分、结构进行了研究，测定了材料的电阻率，对薄膜材料的血液相容性和力学性能进行了系统的研究。结果表明：合成薄膜具有优于热解碳的血液相容性和力学性能，提出了材料的血液相容性机理模型。     

Surface characteristics and bioactivity of oxide film on titanium metal formed by thermal oxidation

In this study, we characterized the surface of oxide film formed on titanium metal through the use of thermal treatment and investigated the effect of surface characteristics on the bioactivity of titanium. The as-received sample group was prepared by polishing and cleaning CP-Ti as a control group, and thermally oxidized sample groups were prepared by heat treating at 530, 600, 700, 800, 900, and 1000°C respectively. Micro-morphology, crystalline structure, chemical composition, and binding state were evaluated using FE-SEM, XRD, and XPS. The bioactivity of sample groups was investigated by observing the degree of calcium phosphate formation from immersion testing in MEM. The surface characterization tests showed that hydroxyl group content in titanium oxide film was increased, as the density of titanium atoms was high and the surface area was large. In MEM immersion test, initial calcium phosphate formation was dependent upon the thickness of titanium oxide, and resultant calcium phosphate formation depended on the content of the hydroxyl group of the titanium oxide film surface.     

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。     

Sol-gel derived hydroxyapatite coatings on titanium substrate

Biomaterials, in particular those used for orthopaedic prostheses, consist of a metallic substrate, exhibiting excellent mechanical properties, coated with a ceramic layer, which guarantees resistance to the corrosion and an elevated bioactivity. In this paper the preparation of sol-gel films of hydroxyapatite, HA (Ca₁₀(PO₄)₆(OH)₂), on titanium substrate is described. The samples were obtained through the dip-coating method, starting from a colloidal suspension of hydroxyapatite. In order to increase the adhesion between the HA film and the metallic substrate, the same substrate has been preliminarily coated either with titanium oxide, TiO₂ (in the anatase or rutile phase), or calcium titanate, CaTiO₃ (perovskite). Also these latter films have been deposited from a sol-gel solution. The characterization of the films through XRD, SEM, and AFM gave good results for the crystallinity of the deposited HA; for what concerns the sample morphology, the films turned out to be homogeneous and crack-free.     

Low-temperature deposition of rutile film on biomaterials substrates and its ability to induce apatite deposition in vitro

Low-temperature deposition of crystalline titania films on intrinsically bioinert materials to induce the bioactivity is of practical interest, not only because it meets the demand of providing organic biomaterials with bioactivity, which cannot tolerate high-temperature thermal treatments, but also because it reserves abundant Ti–OH groups facilitating the apatite deposition. In this paper, rutile films with thickness varied from 0.1 μm to 1.7 μm were deposited on commercially available pure titanium substrates from 1.5 M titanium tetrachloride aqueous solution kept at 60 °C for 3–60 h. The rutile films grew to give a preferred (101) crystalline plane in the X-ray diffraction pattern. After soaking in a simulated body fluid of the Kokubo solution (SBF) for 2 days, the rutile films with thickness over 0.6 μm were covered with a layer of apatite. All the films with various thickness induced apatite deposition in SBF after soaking for 5 days. The bioinert polytetrafluoroethylene (PTFE) was also found to exhibit remarkable in vitro bioactivity as to induce apatite deposition from SBF within 2 days, after depositing the rutile film on the surface. This work is supported partly by the Natural Science Foundation of Zhejiang Province under the project No. M503011.     

Undoped and Cr-doped TiO2 thin films obtained by spray pyrolysis

Undoped and chromium doped titanium oxide thin films were fabricated by spray pyrolysis by using a solution of titanium tetrachloride and ethyl alcohol. The films have been deposited on heated glass substrates at 373 K. After annealing for 90 min at 723 K, the initially amorphous films became polycrystalline with a predominant anatase structure and average crystallite sizes depending on dopant (Cr) concentration. The repartition of chromium impurities in the matrix of titanium oxide films, analyzed by electron paramagnetic resonance and X-ray photoelectron spectroscopy showed that the entrance of chromium into the anatase structure is mainly achieved by substitution. A decrease in unit cell parameters ratio (c/a) with the increase of chromium content sustains this assertion. The wetting properties of the titanium oxide films were evaluated from contact angle measurements between de-ionized water and films surface during- and post-irradiation with UV light. The correlation between the concentration of the dopant, film structure, surface morphology and wettability characteristics is discussed.     

Preparation of regularly structured nanotubular TiO2 thin films on ITO and their modification with thin ALD-grown layers

Nanotubular titanium dioxide thin films were prepared by anodization of titanium metal films evaporated on indium tin oxide (ITO) coated glass. A facile method to enhance the adhesion of the titanium film to the ITO glass was developed. An optimum thickness of 550 nm for the evaporated titanium was found to keep the film adhered to ITO during the anodization. The films were further modified by growing amorphous titania, alumina and tantala thin films conformally in the nanotubes by atomic layer deposition (ALD). The optical, electrical and physical properties of the different structures were compared. It was shown that even 5 nm thin layers can modify the properties of the nanotubular titanium dioxide films.