纯钛材与大变形纯钛材微弧氧化-水热合成复合陶瓷膜层的细胞相容性研究

采用微弧氧化-水热法分别在纯钛材及大变形纯钛材表面制备了TiO_2/HA复合陶瓷膜层,从细胞毒性实验、细胞增殖实验、细胞黏附实验等方面评价膜层的细胞相容性。结果表明:纯钛材与大变形纯钛材微弧复合陶瓷膜层均无细胞毒性。与纯钛材微弧复合陶瓷膜层相比,大变形纯钛材微弧复合陶瓷膜层表面粗糙度更适宜,结晶形核的HA晶粒的形状及Ca/P比更接近人骨HA,更能有效促进成骨细胞的黏附和铺展,随着培养时间的延长,成骨细胞双层重叠生长结构更为明显。成骨细胞在大变形纯钛材微弧复合陶瓷膜层表面各时间点的吸光度值均更高,细胞相容性更好。     

镍钛合金的高级氧化法表面改性及其血液相容性研究

通过高级氧化法对NiTi形状记忆合金进行表面改性，SEM和TF—XRD分析证实，羟自由基（·OH）氧化后的NiTi形状记忆合金表面生成了金红石和锐钛矿结构的二氧化钛薄膜。通过测定动态凝血时间、溶血率和研究血小板黏附行为等方法进行了血液相容性评估。结果表明，经高级氧化法表面改性后的NiTi形状记忆合金血液相容性获得了明显的改善。     

铝合金微弧氧化膜纳米TiO_2掺杂机理研究

在含有纳米TiO_2的电解液中对铝合金进行微弧氧化处理,用以研究掺杂纳米TiO_2对铝合金微弧氧化成膜机理及性能的影响。利用扫描电镜(SEM)观察微弧氧化膜形貌,能谱仪(EDS)分析膜层Ti、Al、O等元素含量,X射线衍射仪(XRD)分析相组成,测定膜厚、硬度和氧化液中TiO_2表面电荷,建立了掺杂改性模型。结果表明,加入纳米TiO_2后,氧化初期电压随TiO_2添加量增加逐渐升高、5min后电压逐渐降低;氧化膜表面孔洞数量和尺寸减小,成膜效率、膜层致密度和表面疏松层硬度提高。纳米TiO_2在氧化膜表面均匀分布,截面不均匀分布。氧化膜主要由γ-Al_2O_3、Mullite和少量Si组成。     

粒子掺入微弧氧化抗菌膜层研究进展

生物医用材料具有优异的力学性能、稳定性及生物相容性等特点,被广泛应用于牙科、骨科、医疗器械等领域。但生物医用材料在使用中易出现各种感染问题,危害人体健康。微弧氧化能够在钛基、镁基等生物医用材料表面构建抗菌膜层,是有效解决感染问题的表面改性技术之一。本文概述了粒子掺入微弧氧化膜层的国内外研究现状及机理,重点综述了近年来Ag、Ag2O、Cu、CuO、ZnO及其它金属氧化物粒子掺入微弧氧化膜层构建抗菌表面的最新研究动态,阐述了粒子掺入对微弧氧化膜层耐蚀性、耐磨性的影响,并对粒子掺入微弧氧化抗菌膜层的应用和发展进行了展望。     

大变形纯钛微弧氧化膜层的生物摩擦学性能研究

采用微弧氧化法在纯钛及大变形纯钛表面制备多孔氧化膜层,研究微弧氧化膜层在干摩擦、模拟体液和小牛血清不同润滑介质条件下的生物摩擦学性能,探讨钛基材组织细化对其膜层表面摩擦磨损性能的影响。结果表明：与纯钛微弧氧化膜层相比,大变形纯钛微弧氧化膜层耐磨性能更优的原因在于钛基材晶粒的细化使得晶体缺陷增多,为微弧氧化膜层的形核提供了更多的能量,反应生成的TiO2膜层硬度更强,膜层表面更致密均匀光滑,提高了其摩擦磨损性能所致。大变形纯钛微弧氧化膜层在小牛血清润滑时的摩擦系数和磨损程度都优于干摩擦和模拟体液润滑条件下的摩擦系数与磨损情况。这归因于小牛血清于摩擦表面形成的化学反应膜及物理吸附膜,起到了更有效的润滑、冷却与承载作用。     

大变形纯钛微弧氧化膜层的生物摩擦学性能

采用微弧氧化法在纯钛及大变形纯钛表面制备多孔氧化膜层,研究微弧氧化膜层在干摩擦、模拟体液和小牛血清不同润滑介质条件下的生物摩擦学性能,探讨钛基材组织细化对其膜层表面摩擦磨损性能的影响。结果表明:与纯钛微弧氧化膜层相比,大变形纯钛微弧氧化膜层耐磨性能更优的原因在于钛基材晶粒的细化使得晶体缺陷增多,为微弧氧化膜层的形核提供了更多的能量,反应生成的Ti O_2膜层硬度更高,膜层表面更致密、均匀、光滑,提高了其摩擦磨损性能。大变形纯钛微弧氧化膜层在小牛血清润滑时的摩擦系数和磨损程度都低于干摩擦和模拟体液润滑条件下的摩擦系数与磨损程度。这归因于小牛血清在摩擦表面形成的化学反应膜及物理吸附膜,起到了更有效的润滑、冷却与承载作用。     

冷喷涂制备多孔Ta涂层及生物相容性

目的 提高生物医用钛合金的生物相容性。方法 采用冷喷涂技术在其表面制备了内部多孔且表面粗糙的钽涂层,并对涂层的微观组织、弹性模量、表面粗糙度、孔隙率、相组成等进行表征;通过溶血率实验、动态凝血时间实验、血小板黏附实验和细胞增殖实验等评价其血液相容性。结果 涂层表面粗糙度为24.9μm,孔隙率为12.6%,弹性模量为147 GPa。喷涂后涂层相组成为Ta,涂层与基体的结合强度为24 MPa。TC4钛合金基体和钽涂层2种材料均具有优异的红细胞相容性且2种材料表面的动态凝血程度相似,表明在TC4钛合金表面制备钽涂层后,钽涂层不会影响凝血因子的活性。钽涂层具有更好的防止血小板黏附与变形的性能。在细胞增殖实验中,细胞在钽涂层表面的增殖能力略高于TC4钛合金。结论 多孔钽涂层的弹性模量相对钽块降低了22%。其生物活性高于TC4钛合金基体。     

纯钛材与大变形纯钛材微弧氧化膜层的力学性能研究

采用微弧氧化法在纯钛材及大变形纯钛材表面制备了含钙、磷的多孔氧化膜层,研究膜层的微观形貌、硬度、膜基结合力、滚动摩擦磨损性能等性能,探讨钛基材组织细化对其膜层结构及力学性能的影响。结果表明:与纯钛材微弧氧化膜层相比,大变形纯钛材微弧氧化膜层表面微纳米尺度的孔洞更多,孔隙率更高(10.84%vs.9.68%),孔洞孔径更小(8.67μm vs.9.68μm),表面更平坦,锐钦矿相含量更高(43.13%vs.37.74%),膜-基结合能力更强(17 N vs.8N),摩擦系数较低(0.338 vs.0.358),耐磨性能更优,以上的膜层结构及力学性能的改善归因于其钛基材大变形化提高了晶体缺陷。     

磁控溅射Zr-Ti薄膜的组织结构与血液相容性

通过直流平衡磁控溅射法在NiTiSMA表面生成Zr-Ti膜,用SEM、XRD和XPS分析证实制备的Zr-Ti膜呈现晶带T型结构,组织保持了细小致密的纤维状特征,与基底结合良好,并且出现了少量生物惰性ZrO2和TiO2陶瓷相。通过测定溶血率研究血小板黏附行为,评估血液相容性。结果表明,与NiTi基底相比,Zr-Ti膜的溶血率更低,表面黏附的血小板数量减少,能够改善NiTiSMA基底的血液相容性。最后,对磁控溅射沉积Zr-Ti膜的成膜机理进行了探讨。     

医用钛合金Ti-3Zr-2Sn-3Mo-25Nb表面自组装抗凝血复合涂层的构建及其血液相容性(英文)

为了提高新型近β钛合金Ti-3Zr-2Sn-3Mo-25Nb(TLM)的抗凝血性能,先通过优化溶胶凝胶技术在TLM合金试样表面制备出一层致密、均匀的TiO2薄膜,再结合表面官能化处理和静电层自组装技术,在TiO2薄膜表面构建一个多层肝素功能涂层。通过XRD分析改性处理后TLM合金表面涂层的相组成,借助SEM、AFM研究功能涂层的表面形貌和微观特征,通过动态凝血时间、溶血率、血小板粘附实验对TLM合金表面改性前后的抗凝血性能和血液相容性进行评估。结果表明,经表面肝素化修饰处理后,TLM合金试样表面光滑、平整,同时材料表面的动态凝血时间延长,溶血率明显降低,试样表面粘附的血小板很少且没有被明显激活,TLM合金的抗凝血性能和血液相容性均得到了明显的改善。     

Induced antibacterial capability of TiO2 coatings in visible light via nitrogen ion implantation

In order to enhance the antibacterial ability of titanium components, an antibacterial coating was fabricated on Ti surface by micro-arc oxidation (MAO) and further nitrogen plasma immersion ion implantation (N-PIII). The XPS spectra demonstrated that nitrogen was incorporated into TiO₂ coatings by N-PIII and the nitrogen content on the surface of TiO₂ coatings increased as the N-PIII time increased. Nitrogen-incorporated samples exhibited remarkably increased absorbance in the visible region and the light absorption edge of nitrogen-incorporated samples showed a redshift compared to MAO samples. Escherichia coli and Staphylococcus aureus were seeded on the samples to assess their antibacterial ability. The bacterial experiment demonstrated that nitrogen-incorporated TiO₂ could effectively reduce the bacterial viability in visible light. Thus, the antibacterial TiO₂ coatings fabricated by MAO and further N-PIII might have large potential in the medical and marine fields.     

纳米颗粒增强TiO_2涂层的制备及其防污性能

为提高二氧化钛涂层的防污性能,采用KH-550硅烷改性锐钛矿型TiO_2颗粒,并充分分散于二氧化钛凝胶涂层中。通过降解亚甲基蓝溶液、细菌贴附试验、藻类贴附试验,分别评价了涂层的光催化性能、抗菌性能及抗藻类附着性能,并利用激光共聚焦显微镜及扫描电子显微镜对藻类在涂层表面的附着情况进行分析。结果表明,添加TiO_2纳米颗粒涂层的防污性能较未添加TiO_2纳米颗粒涂层有较大程度的提高。添加粒径为5~10 nm TiO_2颗粒的二氧化钛涂层对小球藻、三角褐指藻及小新月菱形藻的附着降低率分别达到了92.1%、71.5%和62.1%,相较于纯二氧化钛涂层对3种藻类的附着降低率分别提高了29.7%、68.4%和43.5%。TiO_2颗粒的加入可以有效地提高涂层的光催化性能,光催化使得涂层具有亲水、抗菌及自清洁的性能进而有利于提高涂层的防污性能。     

Characterization of plasma-sprayed hydroxyapatite/TiO2 composite coatings

To enhance the bonding between hydroxyapatite (HA) coating and titanium alloy substrate, HA/TiO₂ composite coatings have been fabricatedvia plasma spraying. Bonding strength evaluation, simulated body fluid tests, and cell culturein vitro were carried out to characterize the composite coatings. The results obtained showed that the addition of TiO₂ to HA coating improved the bonding strength of the coating significantly. After being immersed in simulated body fluid (SBF) for a period, the surfaces of HA/TiO₂ composite coatings were completely covered by carbonate-containing apatite, which indicated that the coatings possess good bioactivity. Thein vitro cell culture indicated good cytocompatibility for HA/TiO₂ composite coatings.     

Effect of different structured TiO2 particle on anticorrosion properties of waterborne epoxy coatings

Anticorrosion properties of waterborne epoxy coatings with three structured nano-particles of TiO₂ were investigated and compared. The surface morphology and structure of TiO₂ have been analysed by XRD, SEM and N₂ adsorption–desorption. Corrosion performance of the nano-composite coating was investigated employing electrochemical impedance spectroscopy and salt spray test. Coatings with mesoporous TiO₂ (meso-TiO₂) possessed the best corrosion performance among the coating specimens. The EIS results show that the resistance value of coating with meso-TiO₂ was above 5.4?×?10⁸?Ω?cm² which was higher than the other nano-composite coatings. Possible strong interactions between polymeric matrix and meso-TiO₂ caused high barrier properties.     

Microstructure and bioactivity of Ca, P and Sr doped TiO2 coating formed on porous titanium by micro-arc oxidation

In the present study, bioactive coatings enriched with micro-pores and Ca-P-Sr elements were formed on pore walls of porous titanium by micro-arc oxidation (MAO). It is found that pore size plays a significant role on the MAO treatment of porous titanium. For samples with pore size smaller than 90 μm, whatever applied voltage and treatment time were employed, MAO coatings were formed only in the near surface region. As to the sample with average pore size of 150 μm, MAO coatings were formed on both outer and inner pore walls throughout the depth. Compared with the untreated one, the specific surface area dramatically increased about 460 times. Further studies found that pore size, thickness and amounts of O, Ca, P and Sr elements of the coating on the outer pore walls were obviously higher than those on the inner pore walls. Additionally, the coating on the outer pore walls was composed of anatase and rutile TiO₂ and other complex Ca-P-Sr phases, in comparison with anatase TiO₂ formed on the inner pore walls. In spite of the distinct features of coatings on the different locations of pore walls, MAO-treated porous titanium overall showed a good apatite-inducing ability.     

Osteoblast growth behavior on micro-arc oxidized β-titanium alloy

β-titanium (β-Ti) alloys are known for their excellent physical properties and biocompatibility, and are therefore considered as next-generation metals for orthopedics and dental implants. To improve the osseous integration between β-Ti alloys and bone, this study develops a titanium dioxide (TiO₂) coating on the surface of β-Ti alloys by using micro-arc oxidation (MAO) technique. The anatase (A) rich and rutile (R) rich TiO₂ layer, were formed on β-Ti, respectively. In vitro tests were carried out using pre-osteoblast cell (MC3T3-E1) to determine biocompatibility and bone formation performance. Biocompatibility includes cell adhesion, cell proliferation, and alkaline phosphatase (ALP) activity, while the bone formation performance contains osteopontin (OPN), osteocalcin (OCN) and calcium content. Cell morphology was also observed. In addition, raw β-Ti, A rich TiO₂ and R rich TiO₂ were implanted into the distal femora of Japanese white rabbits for 4, 8, and 12 weeks to evaluate its in vivo performance.Experimental results show that TiO₂ coating can be grown on and well-adhered to β-Ti. The anatase phase formed under a low applied voltage (350 V), while the rutile phase formed under a high applied voltage (450 V), indicating that crystal structure is strongly influenced by applied voltage. A porous morphology was obtained in the TiO₂ coating regardless of the crystal structure and exhibited superior bone formation performance than β-Ti. In vivo analysis and in vitro test show similar trends. It is also noticeable that the R rich TiO₂ coating achieved better biocompatibility, osteogenesis performance. Therefore, a MAO-treated R rich TiO₂ coating can serve as a novel surface modification technique for β-Ti alloy implants.     

Ti6Al4V钛合金表面Al2O3颗粒改性微弧氧化涂层制备及性能

微弧氧化技术是一门新的表面处理技术,在很多领域有着广泛的应用前景,但其结构受限于电解液成分。本文通过在磷酸盐电解液中加入Al2O3陶瓷颗粒,使得在Ti6Al4V钛合金表面的微弧氧化涂层结构和性能得到改性。涂层的结构和性能通过扫描电镜和XRD衍射仪进行表征和测试,涂层的抗高温氧化性能和热震性能通过高温热循环氧化试验和热震试验进行测试。结果表明,通过在电解液中添加Al2O3陶瓷颗粒,涂层由Al2TiO5 and TiO2组成,涂层更为致密,表现出更为优异的抗高温氧化和热震性能。电解液中游动的Al2O3陶瓷颗粒在微弧氧化过程中被吸入到样品表面并进入涂层,涂层的结构和性能得到改性。     

钛合金表面GO/HA/MAO复合膜层的制备及其性能

为了改善钛合金种植体在体液中的腐蚀及摩擦腐蚀行为,延长其在人体环境中的服役时间,在微弧氧化 (MAO)膜层上采用溶胶凝胶(Sol-gel)法于羟基磷灰石(HA)和氧化石墨烯(GO)的混合溶胶中浸渍提拉成膜,从而在 Ti6Al4V 合金表面成功地制备了 GO/ HA/ MAO 复合膜层。 结果表明,MAO 膜层表面的微孔及微球被 GO/ HA 薄膜有效的覆盖且较为致密;膜层的物相组成主要为金红石相及锐钛矿相的 TiO₂、HA、SiO₂ 和GO;根据电化学腐蚀和摩擦腐蚀结果分析知,GO/ HA/ MAO 复合膜层在模拟体液(SBF)中的耐蚀性及耐摩擦腐蚀性相比于 MAO 膜层和 Ti6Al4V 基体均得到了显著提高。     

Characterization and blood compatibility of TiCxN1 − x hard coating prepared by plasma electrolytic carbonitriding

A novel technique to form Ti(C, N) on titanium, named as plasma electrolytic carbonitriding (PEC/N) on cathode was successful used to prepare TiC_xN_1 − x coating. The structure, composition and morphology of the coating were characterized by XRD, XPS and SEM, respectively. The results indicated that TiC_0.3N_0.7 as a new species appears on the surface of the titanium plate, and the thickness of the coating with porous surface morphology increases with the treated time. The blood compatibility of the TiC_0.3N_0.7 coating was evaluated by haemolysis ratios, dynamic blood clotting test, plasma recalcification time and platelet adhesion. The results indicated that the blood compatibility of the plasma-treated titanium with TiC_xN_1 − x coating is significantly improved as compared to the original titanium. Additionally, the results derived from measurements of hardness and corrosion indicated that the coating has excellent mechanical and corrosion-resistant properties.     

Effect of TiO2 nanoparticles on anticorrosion property in amorphous Ni-P-Cr composite coating in artificial seawater and microbial environment

To obtain the composite with a function of corrosion resistance in seawater and microbial environment, we apply low toxic electrolyte which contained Cr³⁺ instead of Cr⁶⁺ as a chromium source to produce Ni-P-Cr/TiO₂, Ni-P-Cr/ZrO₂ nanocomposite coatings, and Ni-P-Cr/TiO₂ microcomposite coating using direct current (DC) electrodeposits technique. The surface morphology, texture, and composition of the composite coatings are characterized by SEM, XRD, and EDX measurements, respectively. The corrosion behavior of the composite coatings is evaluated by polarization curves and electrochemical impedance spectroscopy (EIS). The results with more positive-shifting E_corr, lowest i_corr, and relatively high value of polarization resistance (R_p) proved that compared with other composite coatings, Ni-P-Cr/TiO₂ nanocomposite coating with its better passive film and unique antibacterial activity caused by TiO₂ nanoparticles incorporated, displayed excellent antibacterial and corrosion resistance property, consistent to the phenomenon that corrosion of this nanocomposite coating in SRB culture medium is not observed.