Ti6Al4V表面纳米多孔氧化膜的电解制备及形成机理研究

在(NH4)2SO4/NH4F电解液中,采用阶段升压至预定电压,然后恒压阳极氧化在Ti6Al4V表面制备出纳米多孔氧化膜。利用SEM、XRD对纳米多孔氧化膜进行表征。研究表明,电解液pH值和外加电压对纳米多孔氧化膜形成和形貌影响非常大。电解液的pH值=4.0,恒压为20V时,形成孔均匀规整的纳米多孔氧化膜,孔内径约为85nm。纳米多孔氧化膜形成机理是:首先钛合金表面钝化,在F-作用下钝化表面发生孔蚀而形成原始胚胎孔,然后胚胎孔处氧化膜在电场支持下发生场致溶解而成大孔。     

纳米多孔铝阳极氧化膜的形成机理研究

为探讨多孔铝阳极氧化膜的形成机理,研究了不同气压条件下铝在磷酸溶液中的阳极氧化过程,发现在真空下进行阳极氧化,氧气析出非常明显。通过测定不同气压下的阳极氧化曲线,分析了致密膜向多孔氧化铝膜的转化和生长过程,结果显示氧气析出是导致氧化膜从致密膜向多孔膜转变的主要原因。提出了在氧化膜/电解液界面上氧气分子的聚集是造成表面条纹的新观点。通过氧化膜断面的SEM形貌表征,首次发现多孔膜的主孔道中存在分孔道。分孔道的产生说明析氧反应不但在致密膜/电解液界面发生,而且在多孔膜孔壁/电解液界面也同时发生。     

阳极氧化法制备有序纳米多孔氧化铝膜的研究

利用电化学阳极氧化的方法,在草酸溶液中,精确控制反应条件,在高纯铝片表面有序生长了纳米多孔氧化铝膜。试验中,分别采用一次阳极氧化和二次阳极氧化方法制备氧化铝膜。利用H3PO4溶液浸泡法对氧化铝膜进行扩孔处理。通过扫描电子显微镜对样品进行表征分析。结果发现,二次阳极氧化制备的氧化铝膜的孔洞分布较一次氧化的更为规则有序,并且孔径大小均匀一致。扫描电镜观察显示,氧化铝膜的扩孔过程可以去掉阻碍层,并调节孔径大小,溶去二次氧化后黏附在氧化层表面的一些杂质,从而使氧化铝模板更为规则有序,孔径均一。这种经过二次阳极氧化和扩孔处理得到多孔阳极氧化铝模板的方法简单,成本较低,可以为后续的纳米材料合成提供高质量的合成模板。     

纳米氧化铝有序多孔膜制备工艺研究

为了获得大面积有序孔排列以及不同孔径的氧化铝膜,采用二次阳极氧化法可制备大面积有序铝阳极氧化多孔(AAO)膜,着重研究氧化电压、氧化时间、电解液浓度以及扩孔时间对AAO膜孔径大小、膜层厚度和形貌结构的影响,用X射线粉末衍射(XRD)仪进行物相分析,利用扫描电子显微镜(SEM)表征多孔膜的形貌.结果表明,在700 ℃以下条件下AAO膜以无定形态存在,经800 ℃退火后无定形氧化铝转化为γ-Al2O3,多孔膜随电压和电解液浓度增加而增大,经H3PO4溶液扩孔后可获得较大孔径模板,扩孔时间与孔径变化呈近似线性关系.为满足应用需求的AAO膜的制备提供了依据.     

阳极氧化法制备纳米级多孔氧化铝膜的研究

比较了电化学抛光前后铝片表面的微观结构,用阳极氧化法制备了纳米级多孔氧化铝膜,用扫描电镜研究分析了氧化铝膜孔的排列规律.结果表明其排列高度有序,呈理想的六方柱形结构.     

阳极氧化制备TiO2纳米多孔膜

分别在氢氟酸和硫酸两种电解液体系下对纯钛(TA1)试样进行阳极氧化,在钛的表面获得TiO2纳米多孔膜.利用膜的颜色的不同来判断膜的厚度的变化,用FESEM观察了孔的形貌和结构并用XRD测试了TiO2膜的晶型,进而研究了阳极氧化电压对孔径和多孔膜晶型的影响并对多孔膜的形成机理进行了阐述.     

纳米多孔阳极氧化铝膜形貌的控制研究

采用38g／L的草酸溶液为电解液,制备了孔洞规则有序,孔径和厚度均一可控的氧化铝模板,并研究了阳极氧化工艺对阳极氧化铝膜形貌的影响。实验结果表明,采用38g／L的草酸溶液作为电解液,经两步法阳极氧化可制得孔径均一,排列规则的多孔阳极氧化铝膜。随着氧化电流密度的升高,氧化膜孔径逐渐增大。电流密度过大,反应放热严重,氧化铝膜孔径均匀性,孔洞形状规则性和有序性都下降。在恒电流密度条件下,氧化膜厚度随着氧化时问的延长呈线性增长,但对氧化铝膜孔径影响较小。     

纳米多孔氧化铝膜的制备

以草酸为电解液,采用二次阳极氧化法于室温下制备了多孔阳极氧化铝膜,研究了电解液浓度和试样退火处理对膜表面形貌的影响.利用扫描电镜(SEM)对其表面形貌进行表征,并对其微观形貌进行分析.结果表明,草酸浓度在0.2～0.4 mol/,L范围内所制备的样品结构符合Keller结构模型,孔洞均匀分布于氧化铝膜表面,纳米孔阵列呈高度有序、紧密堆积的排列,孔径大小一致,约为86 nm,退火处理对膜的形貌没有明显影响.     

工艺参数对冷坩埚连续铸造Ti6Al4V表面的影响

为消除冷坩埚连续成形钛合金铸棒表面缺陷，了解工艺参数对表面质量影响规律，并制备出无裂纹铸棒，通过正交试验和理论分析的方法，研究了不同工艺参数对表面质量的影响，研究表明：表面质量随功率和线圈匝数的增加而变坏，随抽拉速度和拉锭高度的增加先变好后变坏；各参数影响程度不同，线圈匝数影响最大，功率次之，抽拉速度再次，拉锭高度影响最小；铸造表面质量良好钛合金棒的工艺参数为：抽拉速度5mm／min，功率50kW，线圈3匝，拉锭高度30mm。     

多孔氧化铝膜的制备与形成机理的研究概况

直流恒压条件下,酸性溶液中铝的阳极氧化会形成多孔阳极氧化铝(AAO)。其孔径为纳米级且分布均匀,纵横比大,是合成一维纳米材料的理想模板。本文综述了AAO的结构模型、制备方法、形成机理及其应用热点。     

Electrochemical Study of Diffusion Bonded Joints between Micro-duplex Stainless Steel and Ti6A14V Alloy

In the present study,corrosion behavior of diffusion bonded joints formed between micro-duplex stainless steel(MDSS) and Ti6AI4V alloy(TiA)(at 900 ℃ for 60 min under 4 MPa uniaxial pressure in vacuum) was investigated in 1 mol/L HCI and 1 mol/L NaOH solutions using various electrochemical measurements such as open circuit potential(OCP),electrochemical impedance spectroscopy(EIS) and potentiodynamic polarization(PD).For comparison,corrosion behavior of base metals(MDSS and TiA) was also evaluated.Bonded joint was characterized by light optical microscopy and scanning electron microscopy using backscattered electron mode.The layer wise σ phase and λ + FeTi phase mixture has been observed at the bond interface and the bond tensile strength and shear strength were ~556.4 MPa and ~420.2 MPa,respectively.     

In vitro biomimetic deposition of apatite on alkaline and heat treated Ti6A14V alloy surface

Titanium alloy (Ti6A14V) substrates, having the ability of biomimetic calcium phosphate-based materials, especially hydroxyapatite deposition in a simulated body fluid (SBF) means of chemical treatment (alkaline treatment) and subsequent heat treatment, was studied. The effects of alkaline treatment time, concentration and heat treatment temperature on the formation of calcium phosphate (carbonate-hydroxyapatite) on Ti6A14V surface were examined. For this purpose, the metallic substrates were treated in 0, 5 and 10 M NaOH solutions at a temperature of 60 or 80°C for 1 and 3 days. Subsequently the substrate was heat-treated at 500, 600 and 700°C for 1 h for consolidation of the sodium titanate hydrogel layer. Finally, they were soaked in SBF for 1 and 3 days. The substrate surfaces were characterized by the techniques commonly used for bulk material such as scanning electron microscopy (SEM) and thin film X-ray diffraction (TF-XRD). With regard to the SEM and TF-XRD results, the optimum process consists of 3 days soaking in 5 M NaOH in 80°C and subsequent heat treatment at 600°C for 1h. It is worth mentioning that the results showed that the apatite formed within 3 days on the specimen surfaces, however, there was no sign of apatite formation in the control samples (without alkaline and heat treatment) which was treated for up to 3 days immersion in SBF.     

Photo-induced properties of anodic oxide films on Ti6Al4V

Photocatalytic activity and wettability of the anodic oxide layer on Ti6Al4V prepared by anodization in a sulfuric acid electrolyte are explored. The oxide is composed mainly of TiO₂ with V₂O₅, VO₂ and Al₂O₃. The crystal structure of the TiO₂ varies from anatase to rutile with the sulfuric acid concentration in the electrolyte. Anatase exhibits better photocatalytic activity compared with rutile, which is different from those on Ti and Ti-Nb-Sn alloy. Contact angles of the oxides decrease with ultraviolet light illumination, and hydrophilicity is observed in the rutile oxide. Both photocatalytic activity and hydrophilicity are inferior to the corresponding Ti and Ti-Nb-Sn alloy, which is explained by the presence of Al₂O₃ in the anodic oxide.     

Ｔi６A14V等离子体浸没式离子注入

采用新型等离入体浸没式离子注入技术,对Ｔi6A14V合金进行氮离子注入,对注入层的成分,组织和性能的分析表明,注入层中氮浓度的分布具有类高斯分布特征,在注入层中有ＴiN和非态相形态,注入层的显微硬度和摩擦性能得到明显改善。     

Effect of passivation on the dissolution behavior of Ti6A14V and vacuum-brazed Ti6A14V in Hank's ethylene diamine tetra-acetic acid solution Part I Ion release

This work aims to investigate the effects of three factors, namely: (1) two differently prepared materials (as-polished Ti6A14V and 2 h brazed Ti6A14V); (2) three different surface passivation treatments (34% nitric acid passivation, 400°C heated in air, and aged in 100°C de-ionized water); and (3) periods of immersion time (up to 32 days), on trace element release in Hank's ethylene diamine tetra-acetic acid (EDTA) solution. After passivation and autoclaving treatment, the specimens were immersed in 8.0 mM EDTA in Hank's solution and maintained at 37°C for periods of time up to 32 days. The 400°C -treated specimens exhibit a substantial reduction in constituent release, which may be attributed to the higher thickness and rutile structure of the surface oxides. For acid-passivated and water-aged treatments, a highly significant decrease in the trace levels of Ti, A1, and V is detected from the brazed Ti6A14V compared to those obtained from the Ti6A14V specimens. It is hypothesized that an anatase–rutile transformation of surface TiO₂ is likely to occur, accelerated by the elements of copper and nickel in the brazed specimens. In addition, a significant time-related decrease in constituent release rate is observed for all kinds of specimens throughout the 0–8 day experimental period. The implication of the results is discussed. © 1999 Kluwer Academic Publishers     

Factors having influence on the rheological properties of Ti6A14V slurry

A highly porous Ti6Al4V could be produced with a porous polymeric sponge and Ti6Al4V slurry. However, the rheological properties of Ti6Al4V slurry appeared to be the key issue in the preparation of porous Ti6Al4V. In this study, factors having influence on the rheological properties of Ti6Al4V slurry were addressed in detail. Ti6Al4V powders, organic thickening agents (binders), dispersants, concentration of powder and pH values were optimised with regard to the rheological properties of Ti6Al4V slurry. The results show that Ti6Al4V powder with a mean diameter of 45 microm and spherical shape is beneficial for the preparation of Ti6Al4V slurry. Meanwhile binders with two ingredients, which decompose at different temperatures, have the advantage to keep the shape after debinding. The optimised procedure, based on the findings, made it possible to produce highly porous Ti6Al4V with reticulate porous structure. Porous Ti6Al4V produced by this way is expected to be a promising biomaterial for tissue engineering scaffolds and orthopaedic implant applications.     

Ti6Al4V合金ISM熔炼工艺参数优化

利用作者编制的软件模拟了感应凝壳熔炼（ＩＳＭ）Ｔｉ６Ａｌ４Ｖ合金过程,并计算了关键点温度随时间的变化曲线和不同时刻炉料的温度场分布。结果表明,在３－５ｋｇ范围内,炉料越重熔体温度越低,且熔体温度与熔炼功率间存在接近线性的关系。     

Ti、Ti6Al4V和Ti6Al7Nb对成骨细胞生物活性影响的研究

研究Ti、Ti6Al4V和Ti6Al7Nb 3种钛金属表面经喷砂酸蚀处理后的表面形貌、亲水性及对成骨细胞生物活性的影响。在Ti、Ti6Al4V和Ti6Al7Nb 3种钛金属表面进行Al2O3喷砂和盐酸、硫酸混合物酸蚀的表面改性处理(SLA),通过扫描电子显微镜(scanning electron microscope,SEM)观察样品的表面形貌,通过接触角测量仪在显微镜下测量接触角的大小;将SD大鼠成骨细胞以1×104cells/m L密度接种于Ti、Ti6Al4V和Ti6Al7Nb表面后通过MTT活性实验观察成骨细胞在样品表面的增殖,通过SEM观察细胞在样品表面生长的形态,通过碱性磷酸酶(AKP)活性实验,检测成骨细胞的分化能力。Ti、Ti6Al4V和Ti6Al7Nb在经过喷砂酸蚀处理后,表面均呈现出微米级多孔形貌,3种样品均为亲水性表面;细胞在SLA处理后的Ti、Ti6Al4V和Ti6Al7Nb表面增殖良好,细胞伸展显著;其中在Ti6Al7Nb表面细胞的增殖、黏附、分化能力最强。大颗粒喷砂酸蚀技术的表面处理方法能够促进Ti、Ti6Al4V和Ti6Al7Nb的生物活性;经SLA处理的Ti6Al7Nb比Ti和Ti6Al4V表现出更好的生物学活性,成骨细胞在其表面呈现出更好的增殖、黏附及分化能力。