Nanostructured surface changes of Ti-35Ta-xZr alloys with changes in anodization factors

The purpose of this study was to investigate the changes of the nanostructured surface of Ti-35Ta-xZr alloys for dental application resulting from changes in anodization factors. TiO₂ nanotubes were formed on Ti-35Ta-xZr alloys by anodization in H₃PO₄-containing NaF solutions. Anodization was carried out using a scanning potentiostat. Microstructures of the alloys were examined by optical microscopy (OM), field emission scanning electron microscopy (FE-SEM) and x-ray diffraction (XRD). Microstructures of the Ti-35Ta-xZr alloys were changed from α" phase to β phase, and morphologies changed from a needle-like to an equiaxed structure, with increasing Zr content. As the Zr content increased from 3 to 7 to 15 wt.%, the average thickness of the TiO₂ nanotubes increased from 4.5 μm to 6.1 μm to 9.0 μm. When the anodizing potential was increased from 3 V to 10 V, the thickness of the nanotube layers increased from about 0.5 μm to 9.5 μm. As the anodization time increased from 30 min to 180 min at 10 V, the nanotube thickness increased from 4 μm to 9.5 μm. The amorphous oxide phase in the nanotubes transformed to anatase and rutile phases of TiO₂ by heat treatment above 300 °C.     

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.     

Phenomena of nanotube nucleation and growth on new ternary titanium alloys

Ti-30Nb-xZr and Ti-30Ta-xNb alloys have been investigated using various methods of surface nanotube formation. Ternary Ti-30Nb-xZr (x = 3 and 15 wt%) and Ti-30Ta-xNb (x = 3 and 15 wt%) alloys were prepared by using high-purity sponge Ti (Grade 4, G&S Titanium, USA), Ta, Zr and Nb spheres. The two groups of ternary Ti alloys were prepared using a vacuum arc melting furnace. Nanotube formation was carried out with a conventional three-electrode configuration with the Ti alloy specimen, a platinum counterelectrode, and a saturated calomel (SCE) reference electrode. Experiments were performed in 1 M H3PO4 with small additions of NaF (0.1-0.8 wt%), using a potentiostat. Nanotubes formed on the surfaces of the two ternary Ti alloys were examined by field emission scanning electron microscopy, EDS and XRD. The Ti-30Ta-xZr alloys had microstructure with entirely needle-like constituents; the thickness of the needle-like alpha-phase increased as the Zr content increased. The Ti-30Nb-xZr alloys had equiaxed microstructures of the beta-phase, and increasing amounts of the needle-like alpha phase appeared at the grain boundaries of the beta-phase as the Zr content increased. The nanotubes were nucleated and grew mainly on the beta phase for the Ti-30Ta-3Zr and Ti-30Nb-3Zr alloys, which had nanotubes with uniform shape, but the nanotubes were nucleated at the alpha phase for the Ti-30Ta-15Zr and Ti-30Nb-15Zr alloys, which had nanotubes with irregular shape and diameters of two sizes. The diameter and depth of the nanotubes could be controlled, depending upon the alloy composition and composition of the surface oxide films (TiO2, Nb2O5, Ta2O5, and ZrO2). It is concluded that this research that selection of the appropriate alloying element can allow significant control of the nanotopography of these Ti alloy surfaces and that it is possible to control the surface nanotube size to promote long-term osseointegration for clinical dental or orthopedic use.     

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.     

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.     

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.     

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.     

Nanotube morphology changes for Ti-Zr alloys as Zr content increases

Nanotube morphology changes in Ti-Zr alloys as Zr content increases have been investigated. Ti-Zr (10, 20, 30 and 40 wt.%) alloys were prepared by arc melting and heat treated for 24 h at 1000 °C in an argon atmosphere. TiO₂ nanotubes were formed on the Ti-Zr alloys by anodization in H₃PO₄ containing 0.5 wt.% NaF. Electrochemical experiments were performed using a conventional three-electrode configuration with a platinum counter electrode and a saturated calomel reference electrode. Samples were embedded in epoxy resin, leaving an area of 10 mm² exposed to the electrolyte. Anodization was carried out using a scanning potentiostat, and all experiments were conducted at room temperature. Microstructures of the alloys were examined by optical microscopy (OM), field emission scanning electron microscopy (FE-SEM) and x-ray diffraction (XRD). The Ti-Zr alloy microstructures observed by OM and FE-SEM changed from a lamellar structure to a needle-like structure with increasing Zr content. The microstructures also changed from β phase to increasing amounts of α phase as the Zr content increased. The number of large nanotubes formed by anodization decreased, and the number of small nanotubes increased, as the Zr content increased. The mean inner diameter ranged from approximately 150 to 200 nm with a tube-wall thickness of about 20 nm. The interspace between the nanotubes was approximately 60, 70, 100 and 130 nm for Zr contents of 10, 20, 30 and 40 wt.%, respectively.     

Morphology of hydroxyapatite coated nanotube surface of Ti-35Nb-xHf alloys for implant materials

The purpose of this research is to study the morphology of hydroxyapatite coated nanotube surface of Ti-35Nb-xHf for implant materials using various experiments. For this study, Ti-35Nb-xHf (x = 0, 3, 7 and 15 wt.%) alloys were prepared by arc melting and heat treated for 12 h at 1000 °C in an argon atmosphere and then water quenching. Nanotube formation on the Ti-35Nb-xHf alloys was achieved by anodizing in H₃PO₄ electrolytes containing 0.8 wt.% NaF at room temperature. Anodization was carried out using an electrochemical method and all experiments were conducted at room temperature. Hydroxyapatite (HA) was deposited on the nanotubular Ti-35Nb-xHf alloys surface for the biomaterials by radio-frequency (RF) magnetron sputtering method. The morphologies of nanotubular and HA coated surface were characterized by X-ray diffractometer (XRD), optical microscopy (OM), field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM). The wettability of HA coated surface was measured by contact angle goniometer.The microstructure of Ti-35Nb-xHf alloys was transformed needle-like to equiaxed structure with Hf content and α″ phase decreased, whereas β phase increased as Hf content increased. HA coating surface was affected by microstructure of bulk and morphology of nanotube formation. In case of low Hf content, tip of nanotube formed at β phase was coated with HA film, whereas α″ phase was not coated with HA film. In case of high Hf content, nanotube surface was coated uniformly with HA film. The wettability of HA coated nanotubular surface was higher than that of non coated samples.     

Electrochemical characteristics of nanotubes formed on Ti-Nb alloys

Titanium and Ti alloys have been used extensively as bone-implant materials due to their high strength-to-weight ratio, good biocompatibility and excellent corrosion resistance. In this work, we have investigated the effects of the β-stabilizing element Nb on the morphology of nanotubes formed on Ti-xNb alloys using 1.0 M H₃PO₄ electrolyte containing 0.8 wt.% NaF and various electrochemical methods. Oxide layers consisting of highly ordered nanotubes with a wide range of diameters (approximately 55-220 nm) and lengths (approximately 730 nm-2 μm) can be formed on alloys in the Ti-xNb system as a function of Nb content. The nanotubes formed on the Ti-Nb alloy surface were transformed from the anatase to rutile structure of titanium oxide. The titanium oxide nanotube surface was observed to have lower corrosion resistance in 0.9% NaCl solution compared to titanium oxides surfaces on Ti-xNb alloys without the nanotube morphology.     

Fabrication of highly ordered TiO2 nanotube arrays via anodization of Ti-6Al-4V alloy sheet

Uniform and highly ordered TiO2 nanotube arrays were fabricated by the electrochemical anodic oxidation on Ti-6Al-4V surface, using graphite plate as cathode and ethylene glycol (EG) with addition of a certain amount of H2O and NH4F as electrolyte, and the anodization voltage went up to a presetting voltage by stepwise increment. The morphology, structure and composition of TiO2 nanotube arrays were characterized by SEM, EDS, XRD and XPS. The formation process of TiO2 nanotubes was introduced in brief. The experiments were arranged by an orthogonal experiment method and the experimental results showed that the formation of TiO2 nanotube arrays was influenced by not only each factor (F- content, H2O content, external voltage and duration), but also cross correlation among the four factors. The optimal condition was F- content 0.2 wt%, H2O content 4 vol%, external voltage 40 V and duration 1 h in the studied electrochemical system, and the length of obtained nanotubes was 1.5 microm, the outer diameter was approximately 100 nm and the aspect ratio was 15. As-formed nanotube arrays were amorphous and changed to anatase TiO2 after annealed at 500 degrees C for 2 h in air ambience. XPS survey spectra revealed the surface of as-formed nanotube arrays containing Ti, O, C, F and N. The nanotube arrays on Ti-6Al-4V surface with better thermo-stability and crystallinity would have great potential in biomaterials.     

钛合金表面微弧氧化纳米防污涂层及性能研究

利用微弧氧化技术,在Ti-6Al-3Nb-2Zr合金表面成功制备出纳米防污陶瓷涂层。采用扫描电镜、透射电镜和光学显微镜分析了纳米防污涂层的表面形貌、微观形态和氧化层厚度,采用X射线光电子能谱和X射线能谱仪对防污涂层的元素价态和化学组成进行了分析,采用WS-1型划痕试验机和数字万用表研究了涂层的结合强度和绝缘性,并采用TE66微磨损试验机和进行天然海水挂片试验考察了涂层的摩擦学性能和防污性能。结果表明:防污涂层厚度可达到20μm以上,涂层有非晶和20—50 nm纳米晶TiO2及Cu2O构成,膜基结合强度达到50 MPa,涂层绝缘性和耐磨性良好,防污性能得到明显改善,挂片6个月后涂层表面仅有少量海生物附着,而裸钛合金样品挂片3个月后则完全被海生物附着。     

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.     

Oxygen Diffusion Hardening of Ti-Nb-Zr Alloys

Ti-13Nb-13Zr (Ti-13-13^TM) is a new titanium alloy developed for medical implant applications. In the oxygen diffusion hardened condition, Ti-13-13 and titanium alloys which possess zirconium, are hardenable at temperatures of 400 to 600°C with the end result being a passive, mechanically stable, abrasion resistant oxide ceramic surface layer of about 0.2 to 2 μm in thickness. The thickness of this surface layer depends on the concentration of zirconium, time, temperature, and partial pressure of oxygen. This paper describes the results of x-ray diffraction analysis, secondary ion mass spectroscopy, x-ray photoelectron spectroscopy, Knoop and Nano hardness measurements, and reciprocal polarization resistance measurements of hardened Ti-13-13, and selected Ti-Nb-Zr alloys. The results of this work suggest that zirconium plays a key role for effective oxygen diffusion hardening at 500°C for Ti- ] 3-13 and similar Ti-Nb-Zr alloys.     

Vertically oriented Ti-Fe-O nanotube array films: toward a useful material architecture for solar spectrum water photoelectrolysis

In an effort to obtain a material architecture suitable for high-efficiency visible spectrum water photoelectrolysis, herein we report on the fabrication and visible spectrum (380-650 nm) photoelectrochemical properties of self-aligned, vertically oriented Ti-Fe-O nanotube array films. Ti-Fe metal films of variable composition, iron content ranging from 69% to 3.5%, co-sputtered onto FTO-coated glass are anodized in an ethylene glycol + NH4F electrolyte. The resulting amorphous samples are annealed in oxygen at 500 degrees C, resulting in nanotubes composed of a mixed Ti-Fe-O oxide. Some of the iron goes into the titanium lattice substituting titanium ions, and the rest either forms alpha-Fe2O3 crystallites or remains in the amorphous state. Depending upon the Fe content, the band gap of the resulting films ranges from about 380 to 570 nm. The Ti-Fe oxide nanotube array films are utilized in solar spectrum water photoelectrolysis, demonstrating 2 mA/cm2 under AM 1.5 illumination with a sustained, time-energy normalized hydrogen evolution rate by water splitting of 7.1 mL/W.hr in a 1 M KOH solution with a platinum counter electrode under an applied bias of 0.7 V. The surface morphology, structure, elemental analysis, optical, and photoelectrochemical properties of the Ti-Fe oxide nanotube array films are considered.     

Formation of titanium oxide nanotubes using chemical treatments and their characteristic properties

Needle-shaped titanium oxide crystals with a diameter of 8 nm were obtained when titania nanopowders were treated chemically with NaOH aqueous solution and subsequently with HCl aqueous solution under various conditions (e.g., at 110 °C for 20 h). Transmission electron microscopy showed that the needle-shaped products have a tube structure with an inner diameter of approximately 5 nm and an outer diameter of approximately 8 nm. TiO₂ nanotubes with a large specific surface area of ≈ 400 m²/g are expected to have great potentials for use as high-performance photocatalysts or adsorbents. The amount of residual Na⁺ ions in the nanotubes can be controlled by HCl treatment, resulting in the formation of Na-Ti-O titanate nanotubes. The titania and titanate nanotubes can also be modified during the treatment. When calcium acetate solution was used for the treatment, a new type of bioactive nanotube was prepared. An apatite layer was formed on a compact composed of the nanotubes within 1 day of soaking in simulated body fluid. An animal test using rats showed that new-bone-tissue formation around the nanotube compact started 3 days after implantation. When oxoacid solutions, such as perchloric acid, phosphoric acid or sulfuric acid, were used in the treatment, new types of nanotube showing proton conduction were prepared; one of the nanotube compacts showed a high electrical conductivity of 8 × 10^− 2 S/cm at 150 °C. These nanotubes are expected to have applications in the fields of medicine and energy generation, as well as photocatalytic applications.     

Microwave-assisted synthesis and characterization of zinc oxide/carbon nanotube composites

A composite material of zinc oxide and carbon nanotubes were successfully synthesized via a sol process using zinc acetate dihydrate and treated multi-wall carbon nanotubes under microwave irradiation. The morphology, microstructure and chemical bonding of as-obtained composites were well characterized using X-ray diffraction, scanning electron microscope, transmission electron microscope, and Fourier transform infrared spectroscopy. Zinc oxide nanoparticles were dispersively coated on the surface of carbon nanotube when the precursor was dried under microwave irradiation without post-annealing. X-ray diffraction results obviously showed the mixture of two phases of carbon nanotube and wurzite zinc oxide whose size is approximately 15 nm. The formation of zinc oxide nanoparticles on carbon nanotube surface in the composite prepared by microwave heating is much better than the composite heated by conventional annealing. Fourier transform infrared spectroscopic results suggest that carboxylic groups and uniform heating by microwave heating could play key roles on the nucleation of zinc oxide on carbon nanotube surface.     

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.     

Surface characteristics of a porous-surfaced Ti-6Al-4V implant fabricated by electro-discharge-compaction

Electro-discharge-compaction (EDC) is a unique method for producing porous-surfaced metallic implants. The objective of the present studies was to examine the surface characteristics of the Ti-6Al-4V implants formed by EDC. Porous-surfaced Ti-6Al-4V implants were produced by employing EDC using 480 F capacitance and 1.5 kJ input energy. X-ray photoelectron spectroscopy was used to study the surface characteristics of the implant materials. C, O, and Ti were the main constituents, with smaller amounts of Al and V. EDC Ti-6Al-4V also contained N. Titanium was present mainly in the forms of mixed oxides and small amounts of nitride and carbide were observed. Al was present in the form of aluminum oxide, while V in the implant surface did not contribute to the formation of the surface oxide film. The surface of conventionally prepared Ti-6Al-4V primarily consists of TiO₂, whereas, the surface of the EDC-fabricated Ti-6Al-4V consists of complex Ti and Al oxides as well as small amounts of titanium carbide and nitride components. However, preliminary studies indicated that the implant was biocompatible and supports rapid osseointegration.     

Mechanism of surface modification of a porous-coated Ti-6Al-4V implant fabricated by electrical resistance sintering

A porous-coated Ti-6Al-4V implant was fabricated by electrical resistance sintering, using 480 F capacitance and 1.5 kJ input energy. X-ray photoelectron spectroscopy (XPS) was used to study the surface characteristics of the implant material before and after sintering. There were substantial differences in the content of O and N between as-received atomized Ti-6Al-4V powders and the sintered prototype implant, which indicates that electrical resistance sintering alters the surface composition of Ti-6Al-4V. Whereas the surface of atomized Ti-6Al-4V powders was primarily TiO₂, the surface of the implant consisted of a complex of titanium oxides as well as small amounts of titanium carbide and nitride. It is proposed that the electrical resistance sintering process consists of five stages: stage I – electronic breakdown of oxide film and heat accumulation at the metal-oxide interface; stage II – physical breakdown of oxide film; stage III – neck formation and neck growth; stage IV – oxidation, nitriding, and carburizing; and stage V – heat dissipation. The fourth stage, during which the alloy repassivates, is responsible for the altered surface composition of the implant.