Preparation of nanoporous titanium oxide films by electrochemical anodic oxidation

We have investigated the conditions of the formation of tubular layers of nanoporous TiO₂ (NPTO) by the anodic oxidation of Ti in a 1% ammonium fluoride solution in ethylene glycol. The results demonstrate that increasing the anode current density and anodization time increases the nanotube diameter. A model has been proposed for the formation of tubular NPTO layers. The model builds on the concept of anisotropic Ti etching. The rate of the formation of the tubular structure of TiO₂ has been shown to be limited by the oxide film growth rate under the conditions of this study.     

Hydrothermal precipitation of hydroxyapatite on anodic titanium oxide films containing Ca and P

Highly-crystallized hydroxyapatite (HA) can be precipitated during heat treatment in high-pressure steam at 300 °C on an anodic titanium oxide film containing Ca and P (AOFCP), which has been electrochemically formed on a titanium substrate prior to the hydrothermal treatment. Factors affecting the precipitation, such as a percentage of distilled water in the autoclave and additives in the AOFCP, were evaluated by scanning electron microscopy. Ca²⁺ and PO^3– ₄ ions were leached from the AOFCP into a water layer covering the film surface, and nucleate HA heterogeneously on the porous TiO₂ matrix of the AOFCP which was made by the ion leaching. The morphology of the precipitated crystals was significantly affected by the water volume ratio because the concentrations of the Ca²⁺ and PO₄ ^3– ions varied depending on the thickness of the water layer. The amount of the precipitation decreased on the AOFCP which was formed in the solution containing a small amount of Mg²⁺ ions or formed on Ti-6Al-4V alloy instead of titanium.     

Photocatalytic oxidation of nitric oxide with immobilized titanium dioxide films synthesized by hydrothermal method

Gas-phase photocatalytic oxidation (PCO) of nitric oxide (NO) with immobilized TiO2 films was studied in this paper. The immobilized TiO2 films were synthesized by hydrothermal method. The characterization for the physicochemical properties of catalysts prepared under different hydrothermal conditions were carried out by X-ray diffraction analysis (XRD), transmission electron microscopy (TEM), high resolution-transmission electron microscopy (HR-TEM), Brunauer-Emmett-Teller measurements (BET) and scanning electron micrograph (SEM). It was found that the PCO efficiency of the catalyst was mainly depended on the hydrothermal conditions. The optimal values of hydrothermal temperature and hydrothermal time were 200 degrees C and 24 h, respectively. Furthermore, it was also known that the photocatalytic efficiency would decrease remarkably when the calcination temperature was over than 450 degrees C. Under the optimal conditions (hydrothermal condition: 200 degrees C for 24 h; calcination temperature: 450 degrees C), the photocatalytic efficiency of catalyst could reach 60% higher than that of Degussa P25.     

Formation of relatively pure alumina films by anodic polarization

Barrier-type film formation on aluminium in aqueous sodium and potassium hydroxide electrolytes of pH 11 was monitored using transmission electron microscopy of ultramicrotomed sections of the film attached to the substrate. Film growth to relatively low voltages in sodium hydroxide at a constant current density of 50 A m⁻² and associated high current efficiency develops typical barrier-type films of relatively pure alumina, as assessed by Rutherford backscattering spectroscopy, unlike the case with other forming electrolytes in which characteristic anions are generally incorporated in the outer regions of the films. For film growth in potassium hydroxide at a constant current density of 300 A m⁻² to high voltages, which is associated with an overall relatively low current efficiency of formation, an irregular film morphology develops, reminiscent of the appearance of barrier-type films that have suffered dielectric breakdown. In the present situation, where films were formed to voltages less than the breakdown voltage, it is thought that local current concentration, assisted by local heating, contributes to the morphology revealed; “conducting channels” within the film section provide the means for such non-uniform film growth, but precise reasons for their development are not yet clear.     

Room-temperature creep behavior on crack tip of commercially pure titanium

The room-temperature creep behavior on crack tip of compact tensile (CT) specimen for commercially pure titanium (CP-Ti) was studied by experiment and finite element (FE) simulation in this paper. The experimental results indicated that the time-dependent deformation was observed on the crack tip of CP-Ti CT specimen at room temperature, which agreed with the primary creep, and crack propagation was not observed. In order to consider the creep behavior on crack tip, time-dependent J-integral was used to characterize the stress fields near crack tip. The room-temperature creep behavior on crack tip was analyzed by FE simulation, which was verified by experimental results. Then, the strain fields under different stress states were analyzed by FE simulation. The influences of the locations to crack tip and load on the room-temperature creep were analyzed, which shows that the creep significance on crack tip is enhanced with increasing of load and decreasing of distance to crack tip. The estimation formula of creep strain value along ligament direction of CP-Ti CT specimen was established and verified by FE simulation results.     

Osseointegration evaluation of laser-deposited titanium dioxide nanoparticles on commercially pure titanium dental implants

The nanotechnology field plays an important role in the improvement of dental implant surfaces. However, the different techniques used to coat these implants with nanostructured materials can differently affect cells, biomolecules and even ions at the nano scale level. The aim of this study is to evaluate and compare the structural, biomechanical and histological characterization of nano titania films produced by either modified laser or dip coating techniques on commercially pure titanium implant fixtures. Grade II commercially pure titanium rectangular samples measuring 35?×?12?×?0.25?mm length, width and thickness, respectively were coated with titania films using a modified laser deposition technique as the experimental group, while the control group was dip-coated with titania film. The crystallinity, surface roughness, histological feature, microstructures and removal torque values were investigated and compared between the groups. Compared with dip coating technique, the modified laser technique provided a higher quality thin coating film, with improved surface roughness values. For in vivo examinations, forty coated screw-designed dental implants were inserted into the tibia of 20 white New Zealand rabbits’ bone. Biomechanical and histological evaluations were performed after 2 and 4 weeks of implantation. The histological findings showed a variation in the bone response around coated implants done with different coating techniques and different healing intervals. Modified laser-coated samples revealed a significant improvement in structure, surface roughness values, bone integration and bond strength at the bone-implant interface than dip-coated samples. Thus, this technique can be an alternative for coating titanium dental implants.     

Spark plasma sintering behaviour of commercially pure titanium micro-alloyed with Ta-Ru

ABSTRACT

Spark plasma sintering (SPS) technology was used to consolidate Ti-Ta-Ru powders and the effects of sintering parameters on the densification, corrosion and wear performance of the sintered compacts were investigated. Results showed that addition of Ta with small amount of Ru had significant influence on densification, hardness and corrosion behavior of the sintered alloy. When 9 vol.% and 1 vol.% Ru were added, the sintered density and hardness were 92.07% and 330 HV_0.1 respectively. Furthermore, the addition of tantalum and ruthenium improve the corrosion and wear behaviours of Ti with a significant effect on the corrosion potential, E_corr, and corrosion current density, I_corr, in 1?M HCl solution. The COF trend decreases upon the addition of Ta-Ru with relative improvement in wear resistance in Ti-10Ta and Ti-9Ta-1Ru as compared with commercially pure Ti. This decrease in COF is more gradual which may be attributed to the solid solution hardening offered by Ta and Ru in the matrix.     

Ellipsometry of anodic oxide films on tungsten

Non-porous anodic oxide films on tungsten, formed in sulphuric acid and at very low current density (1 mA cm^-2), have been examined using ellipsometry and electron microscopy. Ellipsometry measurements, in conjunction with a suitable computing program, show that the anodic film consists of two layers with slightly different refractive indices, i.e.n₁ = 2.207 and n₂ = 2.322, while the ratio G = d₁/(d₁+d₂) (with d the thickness) of the two layers is 0.509. The rate of growth of the total film thickness as a function of cell voltage at constant current density is constant and equal to 18.4 Å V^-1. Electron microscopy observations confirm these results.     

表面有阳极氧化层的氘化钛热解吸动力学研究

应用反应速率分析方法,测定了氘化钛和表面有阳极氧化层的氘化钛在恒容体系和600～800℃范围内的热解吸反应速率常数,得到氘化钛和阳极氧化的氘化钛热解吸氘的活化能分别为(24.9±1.0)kJ/mol和(38.5±1.2)kJ/mol;氘化钛表面氧化层越厚,表观活化能越大;实验表明氘化钛表面阳极氧化层具有阻氘性能.     

Long-term evaluation of titania-based ceramics compared with commercially pure titanium in vivo

Fifty-four cylinders (2.8 mm in diameter) machined from hot isostatically pressed titania (TI) and titania-hydroxyapatite (TI/HA-15 vol%) sintered at 925°C, as well as commercially pure titanium (c.p. Ti), were implanted in the fermoral cortical bone of New Zealand white rabbits for 1, 3 and 12 months. The shear strength between bone and implant was measured by a push-out test. The TI/HA composite showed a significantly higher bonding strength to bone compared to c.p. Ti at all times, while no differences were observed between TI and c. p. Ti at 1 and 3 months after implantation. Titania-based materials had a significantly higher bonding strength than that of c.p. Ti one year after implantation. The results indicate that bioactivity of HA in TI/HA composite contributes to the early bone apposition reflected by high bonding strength, while the stability of the oxide, determines the development of long-term bonding strength. Both effects may be explained by the level and type of ions released from the ceramic implant. HA has a positive conduction to bone ingrowth while TI has a limited interaction to the bone apposition due to the extraordinary low ion release in vivo. Under light microscopy, similar patterns of bone-implant interfaces were seen from titania-based materials and c.p. Ti in 3-month samples, indicating high biocompatibility of these materials. However, histological evaluation by light microscope cannot identify the differences between physical contact and chemical bonding of implant-bone interface, and thus does not give information on bonding mechanism and the level of shear stresses developed.     

纯钛表面微弧氧化膜纳米压入法研究

微弧氧化是一项较新的等离子体化学-电化学成膜技术，硬度和弹性模量是膜的基本微区力学性能。采用交流微弧氧化方法的铝酸盐溶液中在TA2纯钛表面制备出较厚的氧化膜，利用纳米压入法测定了膜的硬度和弹性膜量，并探讨了微弧放电对氧化膜相组成和性能的影响。研究结果表明：膜的显微硬度和弹性模量分布有相似的变化规律，从膜表层到膜内部，硬度和弹性模量逐渐增加，并在内层膜达到最大值，分别为9.78GPa和176GPa，比钛基体高的多；膜不同浓度处TiO2金红石和TiAl2O5相的相对含量变化决定了硬度和弹性模量的分布。     

Growth of titanium oxide overlayers by thermal oxidation of titanium

This paper describes a theoretical model for the growth of titanium oxide by thermal oxidation of titanium. It is shown that this model can explain the formation of layers of different oxides of titanium and the changes in these layers with variations in the conditions of oxidation. Some experimental X-ray diffraction results which support the model are also given.     

Microstructure of porous anodic oxide films on aluminium

Microstructure of porous anodized films of aluminium prepared in sulphuric acid solution are different from those prepared in an oxalic or phosphoric acid solution. Transmission electron microscopy reveals a multilayer or higher order structure in the former films. Infrared spectra and specific surface area were also studied for these films and new functional properties of the films suitable for new materials were found. In contrast to the fibrous colloidal structure in the cells and barrier layer in the conventional films anodized in a sulphuric acid solution at d.c. 15 V, a network structure is formed in the cells and barrier layer in the hard films prepared at higher voltage of d.c. 25 V. The microstructure changes according to the anodizing conditions. A new model for these sulphuric acid films is presented, i.e. the cell walls are constructed from five layers and the fracture of the films occurs at the centre of the cell walls. Centre barrier layer (4 to 6 nm in thickness) composed of aluminium oxide of high crystallinity was found in a barrier layer at the bottom of the pore, and the thickness is independent on the applied voltage of the anodizing. Increase in thickness of the barrier layer due to applied voltage is governed by that of the outer barrier layer.     

Deposition of titanium/titanium oxide clusters produced by magnetron sputtering

Titanium clusters of nanometer sizes are produced by magnetron sputtering with subsequent aggregation in an argon gas flow. The produced Ti clusters are directed and deposited on a silicon substrate. Deposited films are analyzed by X-ray photoelectron spectroscopy in order to obtain the chemical composition and by atomic force microscopy and X-ray reflection methods to obtain information about the film structure. Experiments were carried out at different temperatures of the walls of the magnetron chamber. The size and the flux of clusters from the magnetron chamber are obtained by the analysis of the substrate surface with deposited clusters. It is found that the cluster parameters strongly depend on the temperature of the magnetron chamber walls. Molecules of titanium oxides may be nuclei of condensation and accelerate the nucleation process. A theoretical analysis based on experimental results is presented. It allows us to describe various stages of cluster evolution from their formation up to the deposition on the substrate and provides estimations for parameters of the processes involving clusters.     

Tailoring the bioactivity of commercially pure titanium by grain refinement using groove pressing

Commercial pure titanium (cpTi) sheets have been processed by groove pressing (GP) at room temperature to refine the grains so as to improve its properties for bone implant applications. Atomic force microscopy revealed submicron/nano roughness features on the processed cpTi. The contact angle measurements show good wettability and higher surface energy when compared to unprocessed cpTi. The bioactivity of the GP samples in simulated body fluid was also found to be enhanced with the formation of a homogenous and dense globular hydroxyapatite layer. The Ca/P ratio of the apatite layer was around 1.66 as similar to the bone mineral phase. The bioactivity enhancement of GP samples has been related to the submicron grain features which results in an increase in the surface roughness and wettability.     

Cytocompatibility of titanium metal injection molding with various anodic oxidation post-treatments

Metal injection molding (MIM) is a near net shape manufacturing method that allows for the production of components of small to moderate size and complex shape. MIM is a cost-effective and flexible manufacturing technique that provides a large innovative potential over existing methods for the industry of implantable devices. Commercially pure titanium (CP-Ti) samples were machined to the same shape as a composite feedstock with titanium and polyoxymethylene, and these metals were injected, debinded and sintered to assess comparative biological properties. Moreover, we treated MIM-Ti parts with BIOCOAT®, BIODIZE® and BIOCER®, three different anodic oxidation techniques that treat titanium using acid, alkaline and anion enriched electrolytes, respectively. Cytocompatibility as well as morphological and chemical features of surfaces was comparatively assessed on each sample, and the results revealed that MIM-Ti compared to CP-Ti demonstrated a specific surface topography with a higher roughness. MIM-Ti and BIOCER® samples significantly enhanced cell proliferation, cell adhesion and cell differentiation compared to CP-Ti. Interestingly, in the anodization post-treatment established in this study, we demonstrated the ability to improve osseointegration through anionic modification treatment. The excellent biological response we observed with MIM parts using the injection molding process represents a promising manufacturing method for the future implantable devices in direct contact with bones.     

Grade-4 commercially pure titanium with ultrahigh strength achieved by twinning-induced grain refinement through cryogenic deformation

The yield strength of commercially pure(CP) Ti of ASTM grade 4, the strongest among all the CP-Ti grades, is too low for structural applications that require high-strength materials. Here, we demonstrate the strengthening of grade-4 CP Ti by cryogenic-temperature rolling(CTR), which enables deformation twinning in grade-4 CP Ti to achieve twinning-induced grain refinement. CTR activated {11.22} twinning and {10.12} twinning, which are the most common twinning systems in pure Ti, whereas room-temperature rolling(RTR) did not activate any twinning system. CTR with imposing an area reduction of just 30% significantly increased the yield strength of the CP Ti to 946 MPa, which is not achievable through typical processes performed at or above room temperature and is comparable to that of commercial Ti-6 Al-4 V. The significant increase in strength was due to microstructural strengthening caused by twinning-induced grain refinement, combined with dislocation accumulation. In contrast to RTR, CTR greatly increased the stress concentration at grain boundaries(GBs), which caused the unusual activation of twinning in the grade-4 CP Ti by facilitating twin nucleation at GBs. The stress concentration increased because CTR activated the slip to a lesser extent compared to RTR, thereby reducing the strain compatibility between neighboring grains. These results will contribute to development of ultrahigh-strength CP Ti and may thereby extend its use to structural applications that require high-strength materials.     

Electrochemiluminescence cell fabrication using TiO2 nanotube produced by anodic oxidation

Electrochemiluminescence (ECL) cell using the electrode of TiO2 nanotube (NT) and Ru(ll) complex Ru(bpy)3(PF6)2 as a luminacence substance was fabricated. TiO2 NT were produced from the membrane of TiO2 NT arrays fabricated by anodic oxidation of approximately 100 microm thick Ti-plate. TiO2 NT arrays inject increasing number of electrons to the Ru(II) complex at the interface of TiO2 NTs. It allows the increasing exergonic oxidation/reduction reaction of Ru(II) complex. The ECL cell emits approximately 600 nm light in orange color. The cell structure is composed of a glass/F-doped SnO2(FTO)/TiO2 NT/Ru(II) complex in propylene carbonate/FTO/glass. The ECL efficiency of the cell consisting of the layer of TiO2 NT was approximately 255 cd/m2 at a bias of 4 V. The use of TiO2 NT increases ECL intensities by 5 times compared to the typical ECL cell without the use of TiO2 NT.     

Application-wise nanostructuring of anodic films on titanium: a review

The interest in titanium and its oxides keeps growing on account of their peculiar engineered properties, which find applications in several fields, from architecture to bioengineering, from automotive to photovoltaic cells and photocatalytic devices, as well as to produce self-cleaning surfaces. This review intends to provide an overview of anodic oxidation treatments currently applied to form nanostructured oxide layers on titanium, with special reference to their whole range of applications. The different procedures and parameters of anodic oxidation will be described, giving information on the main oxide characteristics achievable: thickness, morphology, structure and composition. An analysis of the fields of application associated with specific oxide characteristics will be provided, in order to highlight the variety of properties that can be obtained, and the importance of tuning such properties as a function of the specific application.     

Repeatability of the composition of titanium oxide films produced by evaporation of ti 2 o 3

Congruent vaporization is a process that yields constant vapor species. Ti(2)O(3) was continuously electron-beam evaporated to produce titanium oxide thin films. Rutherford backscattering spectrometry was employed to study the evolution of the composition of these films. It seems that congruent vaporization can be established in a coating plant. TiO(2) films produced by conventional reactive deposition tend to contain mixtures of titanium oxides. Increasing the transmission of TiO(2) films becomes an issue of increasing the TiO(2) component in the films by adequate reactive evaporation.