Fabrication and biocompatibility in vitro of potassium titanate biological thin film/titanium alloy biological composite

A potassium titanate biological thin film/titanium alloy biological composite was fabricated by way of bionic chemistry. The biocompatibility in vitro of Ti-15Mo-3Nb and the potassium titanate biological thin film/titanium alloy was studied using simulated body fluid cultivation, kinetic clotting of blood and osteoblast cell cultivation experiments in vitro. By comparing the biological properties of both materials, the following conclusions can be obtained: (1) The deposition of a calcium phosphate layer was not found on the surface of Ti-15Mo-3Nb, so it was bioinert. Because the network of potassium titanate biological thin film could induce the deposition of a calcium phosphate layer, this showed that it had excellent bioactivity. (2) According to the values of kinetic clotting, the blood coagulation time of the potassium titanate biological thin film was more than that of Ti-15Mo-3Nb. It was obvious that the potassium titanate biological thin film possessed good hemocompatibility. (3) The cell compatibility of both materials was very good. However, the growth trend and multiplication of osteoblast cells on the surface of potassium titanate biological thin film was better, which made for the concrescence of wounds during the earlier period. As a result, the potassium titanate biological thin film/titanium alloy showed better biocompatibility and bioactivity. Translated from Journal of Functional Materials, 2006, 37(10): 1,638–1,642 (in Chinese)     

钛酸钾生物薄膜/钛合金生物复合材料的制备及其体外生物相容性

用仿生化学方法制备钛酸钾生物薄膜/Ti-15Mo-3Nb生物复合材料,然后通过模拟体液培养试验、动态凝血试验及体外细胞培养试验对Ti-15Mo-3Nb和钛酸钾生物薄膜/Ti-15Mo-3Nb生物复合材料的体外生物相容性进行研究,以验证钛酸钾作为一种新型的生物活性涂层材料的可行性.对比试验的结果表明:(1)在模拟体液培养实验中,Ti-15Mo-3Nb表面未见钙磷沉积,表现为生物惰性,而呈多孔网状结构的钛酸钾生物薄膜具有很强的钙磷吸附能力,表现出很好的生物活性;(2)以动态凝血时间为指标,钛酸钾生物薄膜＞Ti-15Mo-3Nb,表现出良好的血液相容性;(3)细胞培养实验表明,二者均具有良好的细胞相容性,但在细胞培养初期钛酸钾生物薄膜具有更好的细胞附壁生长趋势,这将有利于损伤部位的早期愈合.钛酸钾生物薄膜/Ti-15Mo-3Nb生物复合材料表现出更好的生物相容性和生物活性.     

Ti-10Mo-XNb合金铸态组织和机械性能的研究

为了研究Nb元素对Ti-10Mo合金组织和性能的影响,采用钨电极熔化、离心浇注工艺制备了4种钛合金(Ti-10Mo-XNb,X=0,3,7,10),分析并测试了Nb元素对Ti-10Mo合金铸态组织和力学性能的影响.研究结果表明:随着Nb含量的增加,3种Ti-Mo-Nb合金的铸态组织和相组成发生了改变,Ti-10Mo-3Nb合金由等轴的α+β晶粒组成,Ti-10Mo-7Nb合金由等轴的β晶粒组成,Ti-10Mo-10Nb合金由少量等轴和大量枝状的β晶粒组成.另外,随着Nb含量的增加,3种Ti-Mo-Nb合金的维氏硬度、压缩强度、弹性模量降低,压缩率和抗弯强度升高,压缩断口和弯曲断口由脆性断裂向韧性断裂转变.Ti-Mo-Nb合金有望成为新型的生物医用材料.     

Calcium phosphate coating of Ti–Nb–Zr–Sn titanium alloy

This study focuses on rapid formation of calcium phosphate coating on a β type Ti–Nb–Zr–Sn biomedical titanium alloy by alkali treatment. The results show that a bioconductive surface layer forms on specimens immersed in 1–5 M KOH solution but only treatment in 1 M KOH avoids formation of crevices, producing a potassium titanate layer with porous network structure. Heat treatment at 600 °C after the alkali treatment promotes titanate growth. Following the above treatments, a continuous apatite layer forms within 4 h of soaking in a calcium phosphate solution with high ionic concentration. Such rapid apatite formation is due to high concentration of calcium ions in the solution used in this study and the buffering function of NaHCO₃. Results of dissolution experiment show that Ca and P ions release gradually from the coating during soaking in a 0.9% NaCl solution, which may be helpful to the formation of natural bone if implanted in human body. Cell culture experiment shows that the apatite layer favours adhesion and proliferation of rat osteoblast as compared with coating-free Ti–Nb–Zr–Sn alloy and commercially pure titanium (CP Ti).     

In vitro Biological Effects of Ti2448 Alloy Modified by Micro-arc Oxidation and Alkali Heatment

The purpose of this study was to test the hypothesis that the combination of micro-arc oxidation and alkali heatment (MAH) would improve the cytocompatibility of a newly designed Ti-24Nb-4Zr-8Sn alloy.In this study,commercially pure titanium (cp Ti) and Ti-24Nb-4Zr-8Sn were used.Surface modification of Ti-24Nb4Zr-8Sn by a two-step treatment of micro-arc oxidation (MAO) and alkali heatment was reported.Surface characterizations were performed by scanning electron microscopy (SEM),thin film X-ray diffraction (TF-XRD) and X-ray photoelectron spectroscopy (XPS).The MAH layer consisted of finer crystals and possessed a higher degree of crystallity and stability than the MAO layer.A biocompatibility study on treated and untreated Ti24Nb-4Zr-8Sn in comparison with cp Ti was carried out to investigate the effect of the different surfaces on the bone integration property in vitro.The cellular assays revealed that the MAO and MAH layer favored the initial adhesion of MC3T3-E1 cells and that the growth rate of MC3T3-E1 cells on MAH layer was significantly higher than that on the conventional MAO-treated layer after 3-day and 5-day incubation,demonstrating the greater potential of the hybrid treatment of micro-arc oxidation followed with alkali heatment as a novel surface modification method for implanting materials.     

钛合金表面微粗糙化对成骨细胞黏附及增殖行为的影响

采用表面机械研磨(SMAT)法对Ti-25Nb-3Mo-3Zr-2Sn(TLM)钛合金处理15min,而后将处理前后的钛合金样品与成骨细胞共培养1h、24h。采用X射线衍射(XRD)、光学显微镜(OM)、透射电镜(TEM)、扫描电镜(SEM)、电子能谱(EDX)及激光共聚焦显微镜(CLSM)对处理前后样品表面的结构进行了分析,结果显示SMAT处理不会改变TLM钛合金的物相、晶粒尺度及化学组成,处理前后物相均由单一的β相组成,晶粒尺寸均在10~20μm且没有引入新的杂质元素,但SMAT处理会改变TLM钛合金的表面粗糙度,处理前的样品表面平整,平均粗糙度Ra为(0.2±0.03)μm,而处理后的样品表面坑洼不平,平均粗糙度Ra增至(2.6±0.4)μm。随后的细胞实验结果显示,对比SMAT处理前,成骨细胞在处理后的微粗糙表面铺展得更为充分,增殖得更加迅速。研究表明,SMAT处理可以改善TLM钛合金表面的成骨细胞生长环境,从而为开发出更符合临床应用的钛金属种植体提供新的思路。     

Development of a β-type Ti–12Mo–5Ta alloy for biomedical applications: cytocompatibility and metallurgical aspects

Ti-based biocompatible alloys are especially used for replacing failed hard tissue. Some of the most actively investigated materials for medical implants are the beta-Ti alloys, as they have a low elastic modulus (to inhibit bone resorption). They are alloyed with elements such as Nb, Ta, Zr, Mo, and Fe. We have prepared a new beta-Ti alloy that combines Ti with the non-toxic elements Ta and Mo using a vacuum arc-melting furnace and then annealed at 950 degrees C for one hour. The alloy was finally quenched in water at room temperature. The Ti-12Mo-5Ta alloy was characterised by X-ray diffraction, optical microscopy, SEM and EDS and found to have a body-centred-cubic structure (beta-type). It had a lower Young's modulus (about 74 GPa) than the classical alpha/beta Ti-6Al-4V alloy (120 GPa), while its Vickers hardness remained very high (about 303 HV). This makes it a good compromise for a use as a bone substitute. The cytocompatibility of samples of Ti-12Mo-5Ta and Ti-6Al-4V titanium alloys with various surface roughnesses was assessed in vitro using organotypic cultures of bone tissue and quantitative analyses of cell migration, proliferation and adhesion. Mechanically polished surfaces were prepared to produce unorientated residual polished grooves and cells grew to a particularly high density on the smoother Ti-12Mo-5Ta surface tested.     

Influence of noble metals alloying additions on the corrosion behaviour of titanium in a fluoride-containing environment

Titanium alloys exhibit excellent corrosion resistance in most aqueous media due to the formation of a stable oxide film, and some of these alloys (particularly Ti-6Al-7Nb) have been chosen for surgical and odontological implants for their resistance and biocompatibility. Treatment with fluorides (F⁻) is known to be the main method for preventing plaque formation and dental caries. Toothpastes, mouthwashes, and prophylactic gels can contain from 200 to 20,000 ppm F⁻ and can affect the corrosion behaviour of titanium alloy devices present in the oral cavity. In this work, the electrochemical corrosion behaviour of Ti-1M alloys (M = Ag, Au, Pd, Pt) was assessed in artificial saliva of pH = 3.0 containing 910 ppm F⁻ (0.05 M NaF) through open circuit potential, E_OC, and electrochemical impedance spectroscopy (EIS) measurements. The corrosion behaviour of the Ti-6Al-7Nb commercial alloy was also evaluated for comparison. E _OC measurements show an active behaviour for all the titanium alloys in fluoridated acidified saliva due to the presence of significant concentrations of HF and HF₂ ⁻ species that dissolve the spontaneous air-formed oxide film giving rise to surface activation. However, an increase in stability of the passive oxide layer and consequently a decrease in surface activation is observed for the Ti-1M alloys. This behaviour is confirmed by EIS measurements. In fact, the Ti-6Al-7Nb alloy exhibits lower impedance values as compared with Ti-1M alloys, the highest values being measured for the Ti-1Au alloy. The experimental results show that the corrosion resistance of the studied Ti-1M alloys is similar to or better than that of Ti-6Al-7Nb alloy currently used as biomaterial, suggesting their potential for dental applications.     

Biocompatibility studies of human fetal osteoblast cells cultured on gamma titanium aluminide

Ti-48Al-2Cr-2Nb (at. %) (γTiAl), a gamma titanium aluminide alloy originally designed for aerospace applications, appears to have excellent potential for bone repair and replacement. The biological response to γTiAl implant is expected to be similar to other titanium-based biomaterials. Human fetal osteoblast cells were cultured on the surface of γTiAl and Ti-6Al-4V disks with variable surface roughness for both SEM and immunofluorescent analysis to detect the presence of collagen type I and osteonectin, proteins of the bone extracellular matrix. Qualitative results show that cell growth and attachment on γTiAl was normal compared to that of Ti-6Al-4V, suggesting that γTiAl is not toxic to osteoblasts. The presence of collagen type I and osteonectin was observed on both γTiAl and Ti-6Al-4V. The results obtained suggest γTiAl is biocompatible with the osteoblast cells.     

Ti-12Mo-6Zr-2Fe钛合金的纳米压入特征

利用纳米压入测量仪测试了Ti-12Mo-6Zr-2Fe钛合金的硬度和模量.测试表明,Ti-12Mo-6Zr-2Fe钛合金的硬度比Ti-6Al-4V ELI高,而模量比后者低,与常规方法得到的规律一致,表明该方法能很好地表征钛合金的力学特性.对测试过程的分析表明这种方法得到的结果不能与传统方法得到的结果互换,表面状态对测量结果有一定影响.     

Ti-48Al-2Cr-2Nb钝化膜的电化学性能及形成机理

探究Ti-48Al-2Cr-2Nb合金钝化膜的耐腐蚀性和形成机理对提高电解加工过程中的抗杂散腐蚀具有重要意义。通过极化曲线确定了Ti-48Al-2Cr-2Nb合金的钝化电位,采用X射线光电子能谱确定了钝化膜的成分与结构,并运用电化学阻抗谱和Mott-Schottky理论分析了钝化膜的电化学性能。结果表明,Ti-48Al-2Cr-2Nb合金在NaNO3电解液中钝化电位区间为0.079～1.896V,钝化膜主要成分为Al₂O₃、TiO₂及少量的Nb₂O₅,呈双层多孔结构,具有良好的耐腐蚀性。钝化膜具有n型半导体特性,载流子密度随钝化电位的增加而降低。最后,构建了钝化膜形成示意图,揭示了Ti-48Al-2Cr-2Nb合金钝化膜的形成机理与成相膜理论相符,以半球体模型延展并形成独立的相。     

Biomimetic Titanium Alloy with Sparsely Distributed Nanotubes Could Enhance Osteoblast Functions

Designing the bone implant surface by mimicking the structure of natural tissue is an intriguing means to achieve better osseointegration. In this study, a biomimetic surface with sparsely distributed 80 nm diameter nanotubes (SNT) with a spacing of about 20–80 nm from each other, contrary to the closely distributed nanotubes on pure titanium, is fabricated by anodization of near β titanium alloy Ti‐5Zr‐3Sn‐5Mo‐15Nb (TLM). The structure is more similar to the cross‐section of collagen fibrils than commonly reported nanotubes on pure titanium. The SNT‐textured Ti‐alloy also shows good wettability and low elastic modulus more compatible with bone tissues. The surface bioactivity is evaluated in vitro by primary osteoblast cultures. Compared with the polished non‐textured TLM, the SNT texture exhibits satisfactory bioactivity with protein adsorption, initial cell adhesion, cell differentiation as revealed by ALP activity and osteogenesis‐related gene expression. Although cell proliferation is slightly suppressed, ECM deposition is enhanced. The enhanced cell functions are probably related to the biomimetic structure, biochemical characteristics, and mechanical properties of SNT‐textured Ti‐alloy as well as the potential fluid exchange effect among the nanotubes. The SNT texture which constitutes a bio‐interface with fluid supply from the implant surface can be tailored to enhance biological properties such as cell immigration and differentiation.     

New chemical treatment for bioactive titanium alloy with high corrosion resistance

It was recently claimed that titanium metal and its alloys can bond to the living bone, without being coated by apatite (VPS coatings), but by being chemically and heat-treated. The bioactivity of treated titanium is of interest because of the opportunity to obtain orthopaedic or dental implants presenting, at the same time, high toughness, strength and fatigue resistance as well as bone-bonding ability. The bioactive behaviour of the treated implants is due to the presence of a modified surface, which, during soaking in body fluid, promotes the precipitation of apatite. The apatite formed is strongly bonded to the substrate and promotes living bone bonding. In this work were characterised samples of Ti-6Al-7Nb alloy with surfaces presenting a different chemical and mechanical state. The aim of the research was twofold. The first objective was to characterise chemically and heat-treated samples with different surface topography, in order to define the best conditions for osteogenic integration. The second aim was to assess the corrosion behaviour of the bioactive implants, because they expose a microporous and quite thin modified surface layer. No-treated and passivated samples, with a surface state closed to that nowadays used on implants, were used as reference. The surface structure, morphology, electrochemical behaviour and bioactivity of the different samples were assessed by means of XRD, SEM-EDS, anodic polarizations, open circuit measurements and in-vitro tests. Results evidence that it is possible to modify the surface of the Ti-6Al-7Nb alloy in order to obtain the formation of a bioactive layer and that the substrate roughness influences the characteristics of the surface layer formed. It was also evidenced that the as treated surfaces present inadequate corrosion behaviour, so a new two-step chemical treatment has been developed in order to obtain a bioactive material with good corrosion resistance.     

Relationships of strength to composition and phase constitution for three aged beta titanium alloys

X-ray diffraction techniques were used to study properties of three beta titanium alloys in the alpha aged condition. The alloys studied were Beta 111 (Ti-11.5 Mo-6 Zr-4.5 Sn), Beta C (Ti-3 Al-8 V-6 Cr-4 Mo-4 Zr), and 8-8-2-3 (Ti-8 V-8 Mo-2 Fe-3 Al). The volume percentage of alpha phase present and the lattice parameters of both the alpha and beta structures were determined for different ageing treatments. Ultimate tensile strength is related to both alpha content and beta unit cell size in these alloys. However, at high strength levels, beta unit cell size is a more sensitive indicator of tensile strength than percentage of alpha phase. The effects of precipitation hardening mechanisms and alloy partitioning on strengthening are discussed.     

Ti35Nb7Zr-xHA生物复合材料的微观组织与性能研究

为了改善Ti-Nb-Zr合金的生物活性,采用放电等离子烧结(SPS)技术制备了不同羟基磷灰石(HA)含量的Ti35Nb7Zr-xHA(x=0、5、10、20(质量分数,%))生物复合材料,研究了HA含量对复合材料微观组织、力学性能及体外生物活性的影响。结果表明,复合材料主要由β-Ti、α-Ti、HA及陶瓷相(Ti_xP_y、CaTiO_3、Ti_2O、CaO)组成;HA含量增加会导致β-Ti减少而α-Ti和陶瓷相明显增多;与Ti-35Nb-7Zr合金(E:45GPa,σ:1 736 MPa)相比,HA含量为5%和10%时,复合材料的抗压强度分别为1 662MPa和1 593MPa,弹性模量分别为48GPa和49GPa,综合力学性能与Ti-35Nb-7Zr合金接近,展现出良好的力学性能,而过高的HA含量(20%)会导致复合材料弹性模量明显升高(E:55GPa)、抗压强度急剧下降(σ:958 MPa),复合材料的力学性能降低;体外生物活性实验表明,加入10%HA的复合材料在人工模拟体液(SBF)中浸泡7d后表面生成了大量的类骨磷灰石层,与Ti-35Nb-7Zr合金相比,其显示出更优异的体外生物活性。     

Characterization of Sol-gel-derived TiO2 and TiO2-SiO2 Films for Biomedical Applications

In order to improve the corrosion resistance and biocompatibility of NiTi surgical alloy, TiO2 and TiO2-SiO2 thin films were prepared by sol-gel method. The surface characteristics of the film, which include surface composition, microstructure and surface morphology, were studied by X-ray diffraction (XRD), atomic force microscopy (AFM) and X-ray photoelectron spectra (XPS), respectively. A scratching test was used to assess the interface adhesive strength between the film and substrate. The corrosion resistance of NiTi alloy coated with oxide films were studied by anodic polarization curves measurement in biological solution. Additionally, a preliminary study of the in vitro bioactivity of the films was conducted. The results indicated that TiO2 and TiO2-SiO2 (Ti/Si=4:1) films have higher electrochemical corrosion resistance and can be used as protective layers on NiTi alloy. In addition, TiO2-SiO2 composite films have better bioactivity than TiO2 film.     

Controlled oxidative nanopatterning of microrough titanium surfaces for improving osteogenic activity

To further enhance the biological properties of acid-etched microrough titanium surfaces, titania nanotextured thin films were produced by simple chemical oxidation, without significantly altering the existing topographical and roughness features. The nanotextured layers on titanium surfaces can be controllably varied by tuning the oxidation duration time. The oxidation treatment significantly reduced water contact angles and increased the surface energy compared to the surfaces prior to oxidation. The murine bone marrow stromal cells (BMSCs) were used to evaluate the bioactivity. In comparison, oxidative nanopatterning of microrough titanium surfaces led to improved attachment and proliferation of BMSCs. The rate of osteoblastic differentiation was also represented by the increased levels of alkaline phosphatase activity and mineral deposition. These data indicated that oxidative nanopatterning enhanced the biological properties of the microrough titanium surfaces by modulating their surface chemistry and nanotopography. Based on the proven mechanical interlocking ability of microtopographies, enhancement of multiple osteoblast functions attained by this oxidative nanopatterning is expected to lead to better implant osseointegration in vivo.     

Effect of hydrogen charging on microstructural evolution and corrosion behavior of Ti-4Al-2V-1Mo-1Fe alloy

The effect of hydro gen charging on microstructural evolution and corrosion behavior of a Ti-4Al-2V-1Mo-1Fe alloy in a 3.5 wt.% NaCl solution was investigated.The results showed that the hydrogen charging induced the formation and growth of γ-TiH and δ-TiH₂ phases,leading to the initiation and propagation of hydrogen-induced cracks.It was also found that hydrogen charging can change the passivity of this alloy and increase its pitting corrosion susceptibility.The main reason for these was attributed to the fo rmation of hydrides in α phase in the Ti-4Al-2V-1Mo-1Fe alloy,leading to the preferential dissolution of the α phase and thus the deterioration in the protective ability of passive film.     

Fibroblast Adhesion and Proliferation on a New β Type Ti-39Nb-13Ta-4.6Zr Alloy for Biomedical Application

Cell attachment and spreading on Ti-based alloy surfaces is a major parameter in implant technology. Ti-39Nb-13Ta-4.6Zr alloy is a new β type Ti alloy developed for biomedical application. This alloy has low modulus and high strength, which indicates that it can be used for medical purposes such as surgical implants. To evaluate the biocompatibility and effects of the surface morphology of Ti-39Nb-13Ta-4.6Zr on the cellular behaviour, the adhesion and proliferation of rat gingival fibroblasts were studied with substrates having different surface roughness and the results were also compared with commercial pure titanium and Ti-6Al-4V. The results indicate that fibroblast shows similar adhesion and proliferation on the smooth surfaces of commercial pure titanium （Cp Ti）, Ti-39Nb-13Ta-4.6Zr, and Ti-6Al-4V, suggesting that Ti-39Nb-13Ta-4.6Zr has similar biocompatibility to Cp Ti and Ti-6Al-4V. The fibroblast adhesion and spreading was lower on rough surfaces of Cp Ti, Ti-39Nb-13Ta-4.6Zr and Ti-6Al-4V than on smooth ones. Surface roughness appeared to be a dominant factor that determines the fibroblast adhesion and proliferation.     

Nanostructured severe plastic deformation processed titanium for orthodontic mini-implants

Titanium mini-implants have been successfully used as anchorage devices in Orthodontics. Commercially pure titanium (cpTi) was recently replaced by Ti-6Al-4 V alloy as the mini-implant material base due to the higher strength properties of the alloy. However, the lower corrosion resistance and the lower biocompatibility have been lowering the success rate of Ti-6Al-4 V mini-implants. Nanostructured titanium (nTi) is commercially pure titanium that was nanostructured by a specific technique of severe plastic deformation. It is bioinert, does not contain potentially toxic or allergic additives, and has higher specific strength properties than any other titanium applied in medical implants. The higher strength properties associated to the higher biocompatibility make nTi potentially useful for orthodontic mini-implant applications, theoretically overcoming cpTi and Ti-6Al-4 V mini-implants. The purposes of the this work were to process nTi, to mechanically compare cpTi, Ti-6Al-4 V, and nTi mini-implants by torque test, and to evaluate both the surface morphology and the fracture surface characteristics of them by SEM. Torque test results showed significant increase in the maximum torque resistance of nTi mini-implants when compared to cpTi mini-implants, and no statistical difference between Ti-6Al-4 V and nTi mini-implants. SEM analysis demonstrated smooth surface morphology and transgranular fracture aspect for nTi mini-implants. Since nanostructured titanium mini-implants have mechanical properties comparable to titanium alloy mini-implants, and biocompatibility comparable to commercially pure titanium mini-implants, it is suggestive that nanostructured titanium can replace Ti-6Al-4 V alloy as the material base for mini-implants.