Nanotubular surface and morphology of Ti-binary and Ti-ternary alloys for biocompatibility

The nanotubular surface of Ti-binary and Ti-ternary alloys for biomaterials has been investigated using various methods of surface characterization. Binary Ti-xNb (x = 10, 20, 30, and 40 wt.%) and ternary Ti-30Ta-xNb (x = 3, 7 and 15 wt.%) alloys were prepared by using the high-purity sponges; Ti, Ta and Zr spheres. The nanotube on the alloy surface was formed in 1.0 M H₃PO₄ with small additions of NaF (0.5 and 0.8 wt.%), using a potentiostat. For cell proliferation, an MC3T3-E1 mouse osteoblast was used. The surface characteristics were investigated using field-emission scanning electron microscope, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy.Binary Ti-xZr alloys had a lamellar and a needle-like structure, whereas, ternary Ti-30Ta-xZr alloys had equiaxed grains with a lamellar martensitic α′ structure. The thickness of the needle-like laths of the α-phase increased as the Zr content increased. The nanotubes formed on the α phase and β phase showed a different size and shape appearance with Zr content. As the Zr content increased from 3 to 40 wt.%, the diameter of the nanotubes in Ti-xZr and Ti-30Ta-xZr alloy decreased from 200 nm to 50 nm. The nanotubular Ti-30Ta-15Zr alloy surface with a diameter of 50 nm provided a good osseointegration; cell proliferation, migration and differentiation.     

Nanotube morphology and corrosion resistance of a low rigidity quaternary titanium alloy for biomedical applications

Highly ordered nanotube oxide layers were developed on low rigidity quaternary beta-type Ti-35Nb-5Ta-7Zr alloy by controlled anodic oxidation in electrolyte containing 1 M H3PO4 and 0.5 wt% NaF at room temperature. The diameters of the nanotubes formed were in the range of 30 to 80 nm. Electrochemical corrosion behavior of the nanotubular alloy was studied in Ringer's solution at 37 +/- 1 degrees C using potentiodynamic polarization and AC Impedance. The result of the study showed that nanotube formation on the surface affect the passivation behavior of the quaternary alloy significantly. However the corrosion current density was considerably higher for the nanotubular alloy.     

Hydroxyapatite coating on the Ti-35Nb-xZr alloy by electron beam-physical vapor deposition

The aim of this study was to investigate the hydroxyapatite coating on the Ti-35Nb-xZr alloy by electron beam-physical vapor deposition. The Ti-35Nb-xZr ternary alloys contained from 3 wt.% to 10 wt.% Zr content were manufactured by arc melting furnace. Hydroxyapatite (HA) coatings were prepared by electron-beam physical vapor deposition (EB-PVD) method, and crystallization treatment was performed in Ar atmosphere at 300 and 500 °C for 1 h. The coated surface morphology of Ti-35Nb-xZr alloy was examined by FE-SEM, EDX and XRD, respectively. In order to evaluate the corrosion behavior, the tests were performed by potentiodynamic, cyclic polarization and AC impedance test. All the electrochemical data were obtained using a potentiostat. The Ti-35Nb-xZr alloys exhibited equiaxed structure with β phase, the peak of β phase increased with Zr contents. The hardness and elastic modulus of Ti-35Nb-xZr alloys decreased as Zr content increased. The HA coated layer was approximately 150 nm and Ca/P ratio of HA coated surface after heat treatment at 500 °C was around 1.67. The HA thin film consisted of small droplets with spherical shape by crystallization. From the anodic polarization curves, HA coated and heat treated Ti-35Nb-10Zr alloy showed higher corrosion potential than other samples. HA coated film on the Ti-35Nb-10Zr alloy can be shown high polarization resistance by crystallization.     

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. Ti39Nb-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.     

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.     

Electrochemical oxide nanotube formation on the Ti-35Ta-xHf alloys for dental materials

In this study, we investigated the electrochemical oxide nanotube formation on the Ti-35Ta-xHf alloys for dental materials. The Ti-35Ta-xHf alloys contained from 3 wt.% to 15 wt.% Hf were manufactured by arc melting furnace. The nanotube oxide layers were formed on Ti-35Ta-xHf alloy by anodic oxidation method in 1 M H3PO4 electrolytes containing 0.5 wt.% NaF and 0.8 wt.% NaF at room temperature. The surface characteristics of Ti-35Ta-xHf alloy and nanotube morphology were determined by FE-SEM, STEM, and XRD. The nano-porous surface of Ti-35Ta-xHf alloys showed in 0.5 wt% NaF solution and nanotubular surface showed in 0.8 wt% NaF solution, respectively. The highly ordered nanotube layer without regular knots was formed on the Ti-35Ta-15Hf alloy in the 0.5 wt% NaF solution compared to on Ti-35Ta-3Hf and Ti-35Ta-7Hf alloys in 0.8 wt% NaF solution. Also, the nanotube length of Ti-35Ta-xHf alloys increased as Hf content increased.     

Nanotubular oxide surface and layer formed on the Ti-35Ta-xZr alloys for biomaterials

Titanium and its alloys are widely used as a dental implant material in clinical dentistry and as an orthopedic implant materials due to their good mechanical properties, corrosion resistance, and biocompatibility. In this study, nanotubular oxide surface and layer formed on the Ti-35Ta-xZr alloys for biomaterials have been investigated by using electrochemical methods. Ti-35Ta-xZr alloys were prepared by arc melting and heat treated for 24 hr at 1000 degrees C in argon atmosphere, and then water quenching. Ti oxide nanotubes were formed on the Ti-35Ta-xZr alloys by anodizing in H3PO4 containing 0.8 wt% NaF solution at 25 degrees C. Anodization was carried out using a scanning potentiostat. Microstructures of the alloys and nanotube surface were examined by FE-SEM, EDX, and XRD. Crystallization treatment of nanotube surface was carried out for 3 hr at 450 degrees C. Microstructures of the Ti-35Ta-xZr alloys were changed from beta phase to alpha' phase, and changed from an equiaxed to a needle-like structure with increasing Zr content. Nanotubular oxide surface and layers consisting of highly ordered nanotubes with a wide range of diameters (approximately 150-200 nm) and lengths (approximately 4-10 microm) can be formed on alloys in the Ti-35Ta-xZr alloys with Zr content. As the Zr content increased from 3% to 15%, length of step between the bamboo knob-like had increasing values of approximately 50 nm, 80 nm, and 140 nm, respectively. The nanotubes formed on the Ti-35Ta-xZr alloy surface were amorphous structure before heat treatment, but oxide surface had mainly an anatase structure by heat treatment.     

Corrosion behavior of nanotubular oxide on the Ti-29Nb-xZr alloy

This work reports the corrosion behavior of nanotubular oxide layers on Ti-29Nb-xZr alloys with different compositions by anodization in 1 M H3PO4 + 0.8 wt% NaF. Depending on the alloy composition, nanoporous or highly ordered nanotube structures can be formed. The nanotube oxides on the Ti-29Nb-xZr alloy showed lower corrosion current density compared to non-treated sample.     

XPS characterization of surface modified titanium alloys for use as biomaterials

Three different Ti alloys of biomedical interest have been studied by means of X-ray photoelectron spectroscopy (XPS) to determine their surface chemical composition in both as-received condition and after oxidation at 750 °C in air for different times. Compositions of the investigated alloys were, in wt.%, Ti-7Nb-6Al, Ti-13Nb-13Zr and Ti-15Zr-4Nb. XPS analyses showed a behaviour of the Ti-7Nb-6Al alloy different from that of the two TiNbZr alloys, evidencing the role of the chemical composition of the alloys on the oxidation mechanisms. The oxidation process generates an aluminium-oxide rich surface on the Ti-7Nb-6Al, while in the case of the TiNbZr alloys a titanium-oxide rich layer is formed. The effect of the heat treatment on the contribution of the minority elements at the surface is also discussed.     

Structure,mechanical properties,and grindability of dental Ti–Zr alloys

Structure, mechanical properties and grindability of a series of binary Ti-Zr alloys with zirconium contents ranging from 10 to 40 wt% have been investigated. Commercially pure titanium (c.p. Ti) was used as a control. Experimental results indicated that the diffraction peaks of all the Ti-Zr alloys matched those for alpha Ti. No beta-phase peaks were found. The hardness of the Ti-Zr alloys increased as the Zr contents increased, and ranged from 266 HV (Ti-10Zr) to 350 HV (Ti-40Zr). As the concentration of zirconium in the alloys increased, the strength, elastic recovery angles and hardness increased. Moreover, the elastically recoverable angle of Ti-40Zr was higher than of c.p. Ti by as much as 550%. The grindability of each metal was found to be largely dependent on the grinding conditions. The Ti-40Zr alloy had a higher grinding rate and grinding ratio than c.p. Ti at low speed. The grinding rate of the Ti-40Zr alloy at 500 m/min was about 1.8 times larger than that of c.p. Ti, and the grinding ratio was about 1.6 times larger than that of c.p. Ti. Our research suggested that the Ti-40Zr alloy has better mechanical properties, excellent elastic recovery capability and improved grindability at low grinding speed. The Ti-40Zr alloy has a great potential for use as a dental machining alloy.     

Potentiodynamic behaviour of Ti alloys in physiological solution containing lubricant

Ti based alloys are finding wide spread usage in various biomedical applications including joint replacement. The corrosion behaviour of these alloys in simulated body fluid conditions in the presence of lubricant is not reported so far. Thus, present work is undertaken to understand the influence of the lubricant on potentiodynamic behaviour of three types of Ti alloy, namely commercially pure (C.P.) Ti having α structure, Ti-6Al-4Fe having α + β structure and Ti-13Ta-29Nb-4.6Zr having β structure in Ringer's solution. The results show that lubrication does not alter the corrosion rates of single-phase alloys, which have low corrosion rates. However, it significantly reduces the corrosion rates of alloy Ti-6Al-4Fe having α + ß structure.     

In situ X-ray analysis of mechanism of nonlinear super elastic behavior of Ti–Nb–Ta–Zr system beta-type titanium alloy for biomedical applications

Ti–XNb–10Ta–5Zr (mass %) alloys based on nominal compositions of Ti–35Nb–10Ta–5Zr, Ti–30Nb–10Ta–5Zr, and Ti–25Nb–10Ta–5Zr were fabricated through powder metallurgy and forging and swaging processes for biomedical applications. The tensile deformation mechanisms of the Ti–25Nb–10Ta–5Zr, Ti–30Nb–10Ta–5Zr, and Ti–35Nb–10Ta–5Zr alloys were investigated in situ by X-ray diffraction analysis under several loading conditions.Under the loading conditions, the X-ray diffraction peaks of all the specimens shifted to higher angles than those obtained under the unloading conditions. For the Ti–30Nb–10Ta–5Zr alloy, the elastic deformation is considered to progress continuously in a different crystal direction although after the elastic strain reaches elastic limit in the crystal direction where the elastic limit is the smallest, slip deformation occurs in that crystal direction. The elastic modulus of this alloy appears to decrease in terms of strain over the proportional limit. Thus, the elastic deformation behavior of the Ti–30Nb–10Ta–5Zr alloy does not obey Hooke's law.     

Surface characteristics of hydroxyapatite/titanium composite layer on the Ti-35Ta-xZr surface by RF and DC sputtering

The purpose of this study was to investigate the surface characteristics of hydroxyapatite (HA)/titanium (Ti) composite layer on the Ti-35Ta-xZr alloy surface by radio frequency (RF) and direct current (DC) sputtering for dental application. The magnetron sputtered deposition for the HA was performed in the RF mode and for the Ti in the DC mode. Microstructures of the alloys were examined by optical microscopy (OM) and x-ray diffractometer (XRD). Surface characteristics of coated film was investigated by field-emission scanning electron microscope (FE-SEM) equipped with an energy dispersive x-ray spectrometer (EDS), and XRD. Microstructures of the Ti-35Ta-xZr alloys were changed from α″ phase to β phase, and changed from a needle-like structure to an equiaxed structure with increasing Zr content. From the results of polarization behavior in the Ti-35Ta-15Zr alloy, HA/Ti composite layer showed the good corrosion resistance compared to Ti single layer. The results of alternating current (AC) impedance test indicated that the presence of ha coating acted as a stable barrier in increasing the corrosion resistance.     

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。     

Mechanical properties and cyto-toxicity of new beta type titanium alloy with low melting points for dental applications

Beta stabilized new alloys such as Ti–29Nb–13Zr–2Cr, Ti–29Nb–15Zr–1.5Fe, Ti–29Nb–10Zr–0.5Si, Ti–29Nb–10Zr–0.5Cr–0.5Fe and Ti–29Nb–18Zr–2Cr–0.5Si have been developed for dental applications. These alloys were designed based on master alloy Ti–29Nb–13Ta–4.6Zr (TNTZ) for biomedical applications. In this research, high melting temperature element Ta was replaced with beta stabilizing elements such as Cr, Fe and Si to lower the melting temperature of the alloy.Their melting points, mechanical properties, surface reaction layers and cyto-toxicity were investigated in this study.Melting points of designed alloys fall by about 50 K to 370 K as compared with that of TNTZ, and Ti–29Nb–13Zr–2Cr has the lowest melting point of around 2050 K. Vickers hardness of the surface of each designed alloy cast into modified magnesia based investment material is in the range of 400 Hv to 500 Hv, which is lower than that of TNTZ (around 560 Hv).Balances of strength and ductility of cast Ti–29Nb–13Zr–2Cr, Ti–29Nb–15Zr–1.5Fe and Ti–29Nb–10Zr–0.5Cr–0.5Fe are nearly equal to that of cast TNTZ.Cell viability of each cast designed alloy is excellent.     

High‐cycle fatigue properties of beta Ti alloy 55Ti–30Nb–10Ta–5Zr,gum metal

This paper describes the fatigue properties of the beta titanium alloy 55Ti–30Nb–10Ta–5Zr, generally referred to as ‘Gum Metal’. Rotating bending fatigue tests have been performed in laboratory air and in a 3% NaCl aqueous solution. The results obtained were compared with those of a conventional beta titanium alloy, Ti–22V–4Al. In tensile tests, 55Ti–30Nb–10Ta–5Zr indicated elasticity and microplasticity in the elastic region. Thus, the elastic modulus slightly decreased with an increasing strain, and the work hardening was minimal during plastic deformation. The mechanical properties of both of the alloys were comparable. The fatigue strength of 55Ti–30Nb–10Ta–5Zr in laboratory air was higher than that of Ti–22V–4Al, which could be attributed to the higher fatigue crack initiation resistance of 55Ti–30Nb–10Ta–5Zr than Ti–22V–4Al, while the resistance to small fatigue crack growth was similar. The fatigue strength of 55Ti–30Nb–10Ta–5Zr in laboratory air and in the 3% NaCl aqueous solution was analogous. In addition, corrosion pits were not observed in the run‐out specimen in the 3% NaCl aqueous solution, indicating a high resistance of 55Ti–30Nb–10Ta–5Zr against corrosion fatigue.     

Study of the in vitro corrosion behavior and biocompatibility of Zr-2.5Nb and Zr-1.5Nb-1Ta (at%) crystalline alloys

The in vitro corrosion behavior and biocompatibility of two Zr alloys, Zr-2.5Nb, employed for the manufacture of CANDU reactor pressure tubes, and Zr-1.5Nb-1Ta (at%), for use as implant materials have been assessed and compared with those of Grade 2 Ti, which is known to be a highly compatible metallic biomaterial. The in vitro corrosion resistance was investigated by open circuit potential and electrochemical impedance spectroscopy (EIS) measurements, as a function of exposure time to an artificial physiological environment (Ringer’s solution). Open circuit potential values indicated that both the Zr alloys and Grade 2 Ti undergo spontaneous passivation due to spontaneously formed oxide film passivating the metallic surface, in the aggressive environment. It also indicated that the tendency for the formation of a spontaneous oxide is greater for the Zr-1.5Nb-1Ta alloy and that this oxide has better corrosion protection characteristics than the ones formed on Grade 2 Ti or on the Zr-2.5Nb alloy. EIS study showed high impedance values for all samples, increasing with exposure time, indicating an improvement in corrosion resistance of the spontaneous oxide film. The fit obtained suggests a single passive film presents on the metals surface, improving their resistance with exposure time, presenting the highest values to the Zr-1.5Nb-1Ta alloy. For the biocompatibility analysis human osteosarcoma cell line (Saos-2) and human primary bone marrow stromal cells (BMSC) were used. Biocompatibility tests showed that Saos-2 cells grow rapidly, independently of the surface, due to reduced dependency from matrix deposition and microenvironment recognition. BMSC instead display a reduced proliferation, possibly caused by a reduced crosstalk with the metal surface microenvironment. However, once the substrate has been colonized, BMSC seem to respond properly to osteoinduction stimuli, thus supporting a substantial equivalence in the biocompatibility among the Zr alloys and Grade 2 titanium. In summary, high in vitro corrosion resistance together with satisfactory biocompatibility make the Zr-2.5Nb and Zr-1.5Nb-1Ta crystalline alloys promising biomaterials for surgical implants.     

Metastable Beta Titanium Alloys for Orthopedic Applications

This article provides an overview of metastable β titanium alloys either being utilized or being considered for use in orthopedic applications. The effects of thermomechanical processing on the mechanical properties (e.g., elastic modulus, tensile, wear and high cycle fatigue performance) of Ti‐15Mo‐0.2O, Ti‐12Mo‐6Zr‐2Fe (TMZF), Ti‐29Nb‐13Ta‐4.6Zr and Ti‐35Nb‐7Zr‐5Ta are reviewed. The osteointegration behavior of Ti‐29Nb‐13Ta‐4.6Zr and Ti‐35Nb‐7Zr‐5Ta‐O alloys is also presented.     

Precipitates and alloying elements distribution in nearαtitanium alloy Ti65

Precipitates,including silicides and Ti3 Al(α2)phase,and alloying elements distribution in a near a titanium alloy Ti65(Ti-5.8 Al-4.0 Sn-3.5 Zr-0.5 Mo-0.3 Nb-1.0 Ta-0.4 Si-0.8 W-0.05 C)after solution treatment and aging process were characterized by using transmission electron microscopy(TEM)and atom probe tomography(APT).Quantitative composition analysis and TEM observation indicate that the silicides fit to(Ti,Zr)6(Sl,Sn)3.Zr exhibits aβ-stabilizing effect in near a titanium alloys but is weaker than otherβstabilizing elements.The enriching tendency of the alloying elements in the retainedβphase is in the order of Zr相似文献   

Mechanical properties and microstructures of new Ti–Fe–Ta and Ti–Fe–Ta–Zr system alloys

β-type titanium alloys consisting of non-toxic elements, Ti–8Fe–8Ta, Ti–8Fe–8Ta–4Zr, and Ti–10Fe–10Ta–4Zr, were newly designed and developed for biomedical applications. Changes in the mechanical properties of the designed alloys with various heat treatments were discussed on the basis of the resultant microstructures. In addition, the corrosion resistance of the designed alloys was evaluated by polarization testing in Hank's solution. Conventional biomedical titanium (cp-Ti) and the titanium alloy Ti–6Al–4V ELI were also polarized for comparison.The structural phase of the designed alloys, after cold rolling and solution treatment, was only the β phase. Ultimate tensile strength and elongation to fracture of Ti–8Fe–8Ta, Ti–8Fe–8Ta–4Zr, and Ti–10Fe–10Ta–4Zr after solution treatment were 1066 MPa and 10%, 1051 MPa and 10%, and 1092 MPa and 6%, respectively. Ti–8Fe–8Ta and Ti–8Fe–8Ta–4Zr have higher strength than those of conventional biomedical titanium alloys such as Ti–6Al–4V ELI, Ti–6Al–7Nb, and Ti–13Nb–13Zr. In particular, the elongations at failure of Ti–8Fe–8Ta and Ti–8Fe–8Ta–4Zr were equal to those of Ti–6Al–4V ELI and Ti–6Al–7Nb. The designed alloys and conventional biomedical titanium alloys were spontaneously passivated in Hank's solution. The current density of cp-Ti and Ti–6Al–4V ELI was increased at a potential above 2.5 V. On the other hand, the current density of the designed alloys abruptly increased at a potential above 3.5 V. The designed alloys have the advantage over cp-Ti and Ti–6Al–4V ELI in their high resistance to pitting corrosion in biological environments.Therefore, new β-type titanium alloys designed in this study, Ti–8Fe–8Ta and Ti–8Fe–8Ta–4Zr, are expected to have good properties as biomaterials.