镍钛合金表面含银二氧化钛薄膜的水热制备与性能

采用硝酸银溶液对镍钛合金进行水热处理,表面形成了尺寸60～90 nm颗粒的薄膜,分布有约90 nm的含银颗粒。X射线衍射检测到锐钛矿型二氧化钛和单质银的弱衍射峰。X射线光电子能谱分析表明,水热处理形成的二氧化钛薄膜基本覆盖住了镍钛基体,Ag元素以金属态存在。含银二氧化钛薄膜具有较好的紫外光致亲水性。在无钙Hank’s平衡盐液中的动电位极化实验表明,水热处理试样的耐蚀性高于抛光试样,但银的掺入造成阳极极化电流的波动。抛光镍钛试样对葡萄球菌没有抑菌作用,而水热处理试样在暗环境下具有抑菌功能,周围形成了平均宽度约1．2 mm的抑菌圈。     

镍钛合金表面溶胶-凝胶TiO2薄膜的低温制备与固定牛血清白蛋白分子

采用溶胶-凝胶法和蒸汽处理,在经过双氧水粗化预处理的镍钛合金表面制备了无裂纹的TiO2薄膜。X射线衍射表明该薄膜由纳米晶粒的锐钛矿TiO2组成,X射线光电子能谱分析表明试样表面的镍含量大大降低。动电位极化和亲水性测试表明,TiO2薄膜改善了镍钛合金的耐蚀性和亲水性。通过结合3-氨丙基三乙氧基硅烷(APTES)的偶联作用,在TiO2涂层的镍钛合金表面固定了牛血清白蛋白(BSA)分子。     

图像分析方法研究DLC膜/Ti6Al4V梯度材料的血液相容性稳定性

对 DL C膜 / Ti6Al4V梯度材料和 Ti6Al4V钛合金进行了血液相容性稳定性研究。用数字图像分析方法分别测定了材料生物摩擦磨损实验前后的血小板消耗率。研究表明 ,在 Hank' s溶液润滑条件下 ,经过 2 0 0 0 m摩擦磨损实验后 ,Ti6Al4V钛合金血小板消耗率显著增加约 5 0 % ,而 DL C膜 / Ti6Al4V梯度材料血小板消耗率没有明显增加。说明 DL C膜 / Ti6Al4V梯度材料在使用条件下具有很好的血液相容性稳定性     

两种钛合金成品表面特性表征及血液相容性的对比研究

目的对两种不同加工工艺生产的钛合金成品(白色和黑色)进行表面特性鉴定,并评价其血液相容性,为选择合适的工艺流程提供理论依据。方法使用扫描电子显微镜(scanning electron microscopy,SEM)、能谱分析(energy dispersive spectroscopy,EDS)、原子力显微镜(atomic force microscopy,AFM)、X射线衍射仪(X-ray diffraction,XRD)、X射线光电子能谱仪(X-ray photoelectron spectrometer,XPS)对两种钛合金的表面结构、表面物理和化学性能进行表征。通过体外纤维蛋白原吸附、血小板黏附与激活、凝血时间的测定等实验,以及植入狗右心房10 d观察血栓形成情况,系统评价两种钛合金的血液相容性。结果白色钛合金表面为粗且深的犁沟,成分为Ti、Al、V,黑色钛合金表面呈孔样层状叠加分布,且成分除了Ti、Al、V外,还有Si、Na、Ca、Fe等杂质。XRD结果显示两种钛合金物相结构均为钛。XPS结果显示两种钛合金表层都形成极薄的TiO_2薄膜,但黑色钛合金形成的TiO_2薄膜略厚于白色钛合金。体外纤维蛋白原吸附、血小板黏附与激活及凝血时间结果均显示两种钛合金血液相容性无明显差异。体内植入实验结果显示两种钛合金表面均形成了血栓,但黑色钛合金有明显异物反应,形成了增生的肉芽组织,且电镜下显示,白色钛合金表面黏附的有形成分少于黑色钛合金。结论结合体内、体外实验,白色钛合金的生物相容性优于黑色钛合金。     

新型β钛合金Ti_(35)Nb_3Zr_2Ta在人工关节假体应用中的生物相容性

背景:目前被广泛应用于人体关节置换的钛合金为Ti6Al4V,但其弹体模量高于人体骨,导致人工关节假体的稳定性差。而新型β钛合金Ti35Nb3Zr2Ta弹性模量较低,或许能成为新一代生物相容性较好的人体关节假体材料。目的:探讨新型β钛合金Ti35Nb3Zr2Ta在人工关节假体应用的生物相容性。方法:应用计算机检索自万方数据库、中国知网和Pub Med文献数据库,检索时间范围2010至2015年,以"新型β钛合金;人工关节假体;生物相容性"为检索词,检索医用人工关节假体材料的应用现状及新型β钛合金Ti35Nb3Zr2Ta在人工关节假体应用的生物相容性的研究。结果与结论:与Ti6Al4V相比,Ti35Nb3Zr2Ta表面粗糙度较高,表面接触角较小,碱性磷酸酶活性以及成骨细胞的钙沉积量明显高于Ti6Al4V,具有良好的生物相容性,可以考虑在人工关节假体领域中进一步广泛应用。     

电子束熔融法制备的医用Ti6Al4V在人工模拟体液中的耐腐蚀行为

目的研究电子束熔融技术(EBM)3D打印制备的医用Ti6Al4V不同打印截面在Hank's模拟人工体液中的电化学腐蚀行为。方法采用开路电位和动电位极化曲线方法研究了Ti6Al4V不同打印截面,分别记为EBMXOY面(垂直于打印方向的钛合金截面)和EBM-YOZ面(平行于打印方向的钛合金截面),在Hank's模拟人工体液中的电化学腐蚀行为,利用SEM、XRD和金相显微镜分析了其表面形貌和物相组成及其腐蚀机理,并与传统医用锻造Ti6Al4V进行了对比研究。结果与传统医用锻造Ti6Al4V合金相比,EBM-YOZ面钛合金在Hank's模拟人工体液中的开路电位、腐蚀电位和腐蚀电流与之相当,显示出与之接近的耐腐蚀性能;EBM-XOY面钛合金的耐腐蚀性能较EBM-XOZ面和传统锻造钛合金稍差,主要原因是EBM-XOY面的α+β相界面积大,相含量较高,且被优先溶解,因此,耐腐蚀性能较差。结论电子束熔融制造的Ti6Al4V不同截面的耐腐蚀性能不同,EBM-YOZ面的耐腐蚀性能与传统医用锻造钛合金相当,EBM-XOY面的耐腐蚀性能稍差。     

聚多巴胺辅助溶胶-凝胶TiO_2薄膜表面固定牛血清白蛋白

在钛表面涂覆溶胶-凝胶TiO2薄膜,再利用聚多巴胺薄膜结合牛血清白蛋白(BSA)分子,以改善血液相容性。X射线光电子能谱分析表明TiO2薄膜表面形成了聚多巴胺薄膜和BSA分子层。接触角测试结果表明聚多巴胺薄膜和BSA分子层使试样的接触角升高,但表面能和界面张力下降。血液相容性实验表明,与TiO2涂层试样相比,结合BSA分子的试样具有更好的抗凝血性能和抗血小板聚集性能。     

电子束熔融制造医用Ti6Al4V在人工模拟体液中耐腐蚀行为

目的 研究电子束熔融技术（EBM）3D打印制备的医用Ti6Al4V不同打印截面在Hank''s模拟人工体液中的电化学腐蚀行为。方法 采用开路电位和动电位极化曲线方法研究了Ti6Al4V不同打印截面,分别记为EBM-XOY面（垂直于打印方向的钛合金截面）和EBM-YOZ面（平行于打印方向的钛合金截面）,在Hank''s模拟人工体液中的电化学腐蚀行为,利用SEM、XRD和金相显微镜分析了其表面形貌和物相组成及其腐蚀机理,并与传统医用锻造Ti6Al4V进行了对比研究。结果 与传统医用锻造Ti6Al4V合金相比,EBM-YOZ面钛合金在Hank’s模拟人工体液中的开路电位、腐蚀电位和腐蚀电流与之相当,显示出与之接近的耐腐蚀性能;EBM-XOY面钛合金的耐腐蚀性能较EBM-XOZ面和传统锻造钛合金稍差,主要原因是EBM-XOY面的α+β相界面积大,α相含量较高,且被优先溶解,因此,耐腐蚀性能较差。结论 电子束熔融制造的Ti6Al4V不同截面的耐腐蚀性能不同,EBM-YOZ面的耐腐蚀性能与传统医用锻造钛合金相当,EBM-XOY面的耐腐蚀性能稍差。     

HAF/YSZ梯度复合涂层的制备及结构和性能

背景：在钛合金基体表面制备涂层的方法多为等离子喷涂法、溶胶-凝胶法、离子束溅射法等,所制备的涂层性能不稳定、成分单一,且涂层物相组成较难控制。 目的：采用射频磁控溅射技术在Ti6Al4V基体上制备含氟羟基磷灰石梯度复合涂层HAF/YSZ。 方法：在Ti6Al4V基体上以射频磁控溅射技术制备含氟羟基磷灰石梯度复合涂层HAF/YSZ,利用X射线光电子能谱、扫描电镜等对涂层的成分分布、形貌、界面结合进行表征。通过模拟体液实验分析和评价HAF/YSZ涂层、HAF1.2涂层及羟基磷灰石涂层的生物性能。 结果与结论：所制备的HAF/YSZ梯度涂层表面粗糙,呈多孔岛状结构,有利于新生骨组织生长;涂层与基体结合紧密,各层间相互扩散,整体一致性较好;经模拟体液浸泡后,涂层表面有新生物质沉积,表现出较好的生物活性及稳定性,且梯度复合涂层较氟含量单一的氟羟基磷灰石涂层具有更好的抗体液溶解能力及稳定性。     

植入用Ti-6Al-4V合金模拟体液浸泡后高频和超高周疲劳性能

目的为预测植入用Ti-6Al-4V钛合金的使用寿命,研究其在模拟体液浸泡后,107周次以后的超高周疲劳性能。方法将Ti-6Al-4V钛合金试样在模拟体液中分别浸泡2 d和6 d;利用超声疲劳实验技术,在室温下分别对这两组试样进行超高周疲劳性能测试;利用电子显微镜观察疲劳断口并对裂纹源进行X射线能谱分析,研究其裂纹萌生机理,并与未经浸泡的同种材料的超声疲劳性能进行对比分析。结果模拟体液浸泡后的材料的S-N曲线与未经浸泡时的趋势相近,在104～108周次范围内的疲劳寿命都呈连续下降状态,在107～108周次循环范围内曲线下降趋势有所变慢;模拟体液浸泡后的试样在107周次之前寿命下降更快,107周次之后模拟体液浸泡过的试样寿命比未处理的试样寿命低;浸泡6 d后的试样的寿命和浸泡2 d后的相差不大。疲劳循环超过107周次后,仍然发生疲劳断裂,并不存在传统意义上的疲劳极限。疲劳寿命108周次以后的试样疲劳裂纹在内部萌生,一般为铝元素聚集区;疲劳寿命107周次以前裂纹一般萌生于试件表面,有些试件出现了多处裂纹源。结论模拟体液浸泡会降低Ti-6Al-4V钛合金的超高周疲劳性能;随着循环周次的增加,裂纹萌生由试件表面向其内部转换。     

Effects of calcium ion incorporation on bone healing of Ti6Al4V alloy implants in rabbit tibiae

The biocompatibility of calcium ion (Ca)-incorporated Ti6Al4V alloy implants, produced by hydrothermal treatment using a Ca-containing solution, was investigated. The surface characteristics were evaluated by scanning electron microscopy, thin-film X-ray diffractometry, Auger electron spectroscopy, and stylus profilometry. The viability of MC3T3-E1 cells on Ca-incorporated machined Ti6Al4V surfaces with different oxide thicknesses was compared with that on untreated machined Ti6Al4V surfaces with MTT assay. The osteoconductivity of the Ca-incorporated Ti6Al4V implants was evaluated by removal torque testing and histomorphometric analysis after 6 weeks of implantation in rabbit tibiae. Our results show that hydrothermal treatment with a Ca-containing solution produced a crystalline CaTiO(3) layer on Ti6Al4V surfaces, and calcium ions were gradually incorporated throughout the oxide layer. After immersion in Hank's balanced salt solution, a considerable apatite deposition was observed on all surfaces of the Ca-incorporated samples. Significant increases in cell viability (p<0.001), removal torque forces, and bone-to-implant contact values (p<0.05) were observed for Ca-incorporated Ti6Al4V implants compared with those for untreated Ti6Al4V implants.     

Corrosion behavior and biocompatibility of nanostructured TiO2 film on Ti6Al4V

The corrosion behavior and cell adhesion property of nanostructured TiO2 films deposited electrolytically on Ti6Al4V were examined in the present in vitro study. The nanostructured TiO2 film deposition on Ti6Al4V was achieved via peroxoprecursors. SEM micrographs exhibit the formation of amorphous and crystallite TiO2 nanoparticles on Ti6Al4V before and after being annealed at 500 degrees C. Corrosion behavior of TiO2-deposited and uncoated Ti6Al4V was evaluated in freely aerated Hank's solution at 37 degrees C by the measurement and analysis of open-circuit potential variation with time, Tafel plots, and electrochemical impedance spectroscopy. The electrochemical results indicated that nano-TiO2 coated Ti6Al4V showed a better corrosion resistance in simulated biofluid than uncoated Ti6Al4V. Rat bone cells and human aortic smooth muscle cells were grown on these substrates to study the cellular responses in vitro. The SEM images revealed enhanced cell adhesion, cell spreading, and proliferation on nano-TiO2 coated Ti6Al4V compared to those grown on uncoated substrates for both cell lines. These results suggested that nanotopography produced by deposition of nanostructured TiO2 onto Ti alloy surfaces might enhance corrosion resistance, biocompatibility, and cell integration for implants made of Ti alloys.     

Nucleation and growth of apatite on chemically treated titanium alloy: an electrochemical impedance spectroscopy study

Bone-like apatite formed on the surface of Ti6Al4V pretreated with NaOH solution after having been immersed in simulated body fluid (SBF), while no apatite formed on the surface of untreated Ti6Al4V. In the present study, electrochemical impedance spectroscopy (EIS) measurement was used to investigate the nucleation and growth of apatite on chemically treated Ti6Al4V immersed in the SBF solution, and the difference between the behaviors of treated and untreated Ti6Al4V. Appropriate equivalent circuit models were constructed to describe the nucleation and growth of apatite, and thin oxide film formed on the surface of untreated Ti6Al4V. It was found that EIS is a useful method for investigating the nucleation and growth of bone-like apatite on Ti6Al4V pretreated with NaOH solution.     

Thermal oxidation enhances early interactions between human osteoblasts and alumina blasted Ti6Al4V alloy

Oxidation of Ti6Al4V at 500 degrees C for 1 h in air results in the formation of an outer ceramic layer that improves osteoblast behavior and decreases Ti and Al ion release. In this work, alumina blasted Ti6Al4V alloy has been thermally treated and its in vitro biocompatibility has been assessed. Roughness of the blasted alloy was not found significantly altered after heat treatment while chemical surface analysis indicated an increase in stable TiO(2) and Al(2)O(3) oxides. Cell attachment, spreading, cytoskeleton organization as well as cell proliferation, viability, and procollagen I peptide secretion of human primary osteoblasts, impaired on alumina blasted Ti6Al4V, were found to be greatly enhanced on the thermally oxidized blasted alloy. Other informative markers of the osteoblastic phenotype such as alkaline phosphatase, osteocalcin, osteoprotegerin, and mineralized nodule formation were evaluated and indicated that osteoblasts responded at the same extent on untreated and thermally treated blasted alloys. Taken together, our in vitro results indicate that thermal oxidation of alumina blasted Ti6Al4V may favor successful osseointegration by promoting early interactions of osteoblastic cells and the modified surface alloy.     

Osteoblast response and osseointegration of a Ti–6Al–4V alloy implant incorporating strontium

This study investigated the surface characteristics, in vitro and in vivo biocompatibility of Ti–6Al–4V alloy implants incorporating strontium ions (Sr), produced by hydrothermal treatment using a Sr-containing solution, for future biomedical applications. The surface characteristics were evaluated by scanning electron microscopy, thin-film X-ray diffractometry, X-ray photoelectron spectroscopy, optical profilometry, contact angle and surface energy measurement and inductively coupled plasma-mass spectroscopy (ICP-MS). Human osteoblast-like cell (MG63) attachment, proliferation, alkaline phosphatase (ALP) activity, and quantitative analysis of osteoblastic gene expression on Sr-containing Ti–6Al–4V surfaces were compared with untreated Ti–6Al–4V surfaces. Fifty-six screw implants (28 control and 28 experimental) were placed in the tibiae and femoral condyles of seven New Zealand White rabbits. The osteoconductivity of Sr-containing Ti–6Al–4V implants was evaluated by removal torque testing and histomorphometric analysis after 4 weeks implantation. Hydrothermal treatment produced a crystalline SrTiO₃ layer. ICP-MS analysis showed that Sr ions were released from treated surfaces into the solution. Significant increases in ALP activity (P = 0.000), mRNA expressions of key osteoblast genes (osterix, bone sialoprotein, and osteocalcin), removal torque values (P < 0.05) and bone–implant contact percentages (P < 0.05) in both cortical and cancellous bone were observed for Sr-containing Ti–6Al–4V surfaces. The results indicate that the Sr-containing oxide layer produced by hydrothermal treatment may be effective in improving the osseointegration of Ti–6Al–4V alloy implants by enhancing differentiation of osteoblastic cells, removal torque forces and bone apposition in both cortical and cancellous bone.     

Passive film on orthopaedic TiAlV alloy formed in physiological solution investigated by X-ray photoelectron spectroscopy

The passive film formed by electrochemical oxidation on TiAlV alloy in physiological solution was studied using X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The alloy was polarised at different oxidation potentials in the electrochemical chamber attached to the spectrometer. Thus the composition of the layer formed by oxidation was analysed by XPS without prior exposure to air (quasi-in situ). The oxide layer was predominantly TiO2, which contained a small amount of suboxides TiO and Ti2O3 closer to the inner metal/oxide interface. With increasing potential the content of Ti4+ species increased and that of Ti3+ and Ti2+ decreased. The content of titanium in TiO2 was lower than theoretically predicted due to the incorporation of Al2O3 in TiO2 matrix. Vanadium oxide was not identified by XPS. Angular resolved XPS analysis confirmed that Al2O3 is located mainly at the outer oxide/solution interface. The thickness of the oxide layer was dependent on the oxidation potential and after oxidation at 2.5 V reached 9 nm. EIS measurements were used to in situ characterise electronic properties of passive films over seven decades of frequency. A link between electronic, electrochemical and physiochemical properties was established.     

Effect of hydrothermally treated anodic oxide films on osteoblast attachment and proliferation

In this study, the effect of anodization following hydrothermal treatments on osteoblast cell attachment and proliferation were evaluated. The anodic oxide films produced in this study was observed to exhibit overlapping microporous structures with microprojections. In addition, the anodic oxide surfaces were significantly rougher in comparison to control untreated titanium (Ti) surfaces. Following hydrothermal treatments for 2 and 4 h, hydroxyapatite (HA) crystals were observed on anodic surfaces. Using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assay, no significant difference in the biocompatibility of the treated and untreated Ti surfaces was observed. However, scanning electron micrographs indicated rounded osteoblast cells on control and anodized Ti surfaces, with numerous microvilli after 6 h. In contract, cells cultured on hydrothermally treated surfaces after 6 h incubation were observed to exhibit polygonal shape, flattened, and fully spread. In addition, more cells were observed on Ti surfaces that were hydrothermally treated for 4 h as compared to Ti surfaces that were hydrothermally treated for 2 h. After culturing the cells for 24 h and 4 days, no significant difference was observed for cells cultured on all surfaces. It was concluded from this study that hydrothermally treated surfaces exhibited an effect on early osteoblast attachment.     

The response of bone to nanocrystalline hydroxyapatite-coated Ti13Nb11Zr alloy in an animal model

An in vivo study was carried out on uncoated and hydroxyapatite (HA)-coated nanostructured Ti13Nb11Zr alloy in comparison with high-grade Ti6Al4V, to investigate the effect of the different surfaces on osteointegration rate. A highly effective method to obtain a fast biomimetic deposition of a thin layer of nanocrystalline HA was applied to coat both substrates. Cylindrical pins were implanted in rabbit cortical bone and evaluated at 4 and 12 weeks by histomorphometry and microhardness tests. The results confirmed the ability of the slightly supersaturated Ca/P solution to induce a fast deposition of nanocrystalline HA on Ti alloys' surfaces. HA-coated Ti13Nb11Zr had the highest osteointegration rate at 4 and 12 weeks. Both HA-coated surfaces showed an affinity index significantly higher than those of native surfaces at 4 weeks (Ti13Nb11Zr+HA: 37%; Ti6Al4V+HA: 26%). Microhardness test showed a significantly higher bone mineralization index of HA-coated Ti13Nb11Zr in comparison with that of HA-coated Ti6Al4V surface. The study suggests that the HA coating on both alloys enhances bone response around implants and that there is a synergic effect of Ti-Nb-Zr alloy with the HA coating on bone remodeling and maturation.     

Electron beam-melted, free-form-fabricated titanium alloy implants: Material surface characterization and early bone response in rabbits

Titanium-6aluminum-4vanadium implants (Ti6Al4V) were prepared by free-form-fabrication (FFF) and were used either as produced or after machining and compared with wrought machined Ti6Al4V. Auger electron spectroscopy (AES), depth profiles, and interferometry were used to analyze the surface properties. The tissue response after 6-weeks in rabbit femur and tibia was evaluated using light microscopy and histomorphometry. The results revealed that the bulk chemical and mechanical properties of the reference material and the electron beam-melted (EBM) material were within the ASTM F136 specifications. The as-produced EBM Ti6Al4V implants had increased surface roughness, thicker surface oxide and, with the exception of a higher content of Fe, a similar surface chemical composition compared with machined EBM Ti6Al4V and machined, wrought Ti6Al4V implants. The two latter implants did not differ with respect to surface properties. The general tissue response was similar for all three implant types. Histomorphometry revealed a high degree of bone-to-implant contact (no statistically significant differences) for all the three implant types. The present results show that the surface properties of EBM Ti6Al4V display biological short-term behavior in bone equal to that of conventional wrought titanium alloy. The opportunity to engineer geometric properties provides new and additional benefits which justify further studies.