Effect of two-step functionalization of Ti by chemical processes on protein adsorption

Titanium and its alloys are widely used for orthopedic and dental implants because of their superior mechanical properties, low modulus, excellent corrosion resistance and good biocompatibility. However, it takes several months for titanium implants and bone tissue to reach integration. Hence, there is growing interest in shortening the process of osseointegration and thereby reducing surgical restrictions. Various surface modifications have been applied to form a bioactive titanium oxide layer on the metal surface, which is known to accelerate osseointegration.The present work shows that titanium dioxide (TiO₂) layers formed on titanium substrates by etching in a solution of sodium hydroxide (NaOH) or hydrogen peroxide/phosphoric acid (H₃PO₄/H₂O₂, with a volume ratio of 1:1) are highly suitable pre-treatments for apatite-like coating deposition. Using a two-step procedure (etching in an alkaline or acidic solution followed by soaking in Hanks’ medium), biomimetic calcium phosphate coatings were deposited on porous TiO₂ layers. The combined effects of surface topography and chemistry on the formation of the calcium phosphate layer are presented. The topography of the TiO₂ layers was characterized using HR-SEM and AFM techniques. The nucleation and growth of calcium phosphate (Ca-P) coatings deposited on TiO₂ porous layers from Hanks’ solution was investigated using HR-SEM microscopy. AES, XPS and FTIR surface analytical techniques were used to characterize the titanium dioxide layers before and after deposition of the calcium phosphate coatings, as well as after the process of protein adsorption. To evaluate the potential use of such materials for biomedical applications, the adsorption of serum albumin, the most abundant protein in the blood, was studied on such surfaces.     

Surface modification of titanium by nano-TiO2/HA bioceramic coating

A nano-TiO₂/hydroxyapatite composite bioceramic coating was developed and applied to the surfaces of pure titanium discs by the sol-gel method. A TiO₂ anatase bioceramic coating was utilized in the inner layer, which could adhere tightly to the titanium substrate. A porous hydroxyapatite (HA) bioceramic coating was utilized in the outer layer, which has higher solubility and better short-term bioactivity. Conventional HA coatings and commercially pure titanium were used as controls. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were employed to characterize the crystallization, surface morphology, and thickness of the coatings. The bioactivities of the coatings were evaluated by in vitro osteoblast cultures. Results showed that the nano-TiO₂/HA composite bioceramic coating exhibited good crystallization and homogeneous, nano-scale surface morphology. In addition, the nano-TiO₂/HA coating adhered tightly to the substrate, and the in vitro osteoblast cultures exhibited satisfactory bioactivity.     

Comparison of surface films formed on titanium by pulsed Nd:YAG laser irradiation at different powers and wavelengths in nitrogen atmosphere

The nitridation of titanium (Ti) caused by a Q-switched Nd:YAG laser under nitrogen gas atmosphere was investigated in situ using X-ray photoelectron spectroscopy (XPS). A laser having a wavelength of 1064 nm and 532 nm (SHG mode) was irradiated on a titanium substrate in an atmosphere-controlled chamber, and the substrate was then transported to an XPS analysis chamber without exposing it to air. The characteristics of the surface layer strongly depend on the laser power. When the power is relatively low, a titanium dioxide layer containing a small amount of nitrogen is formed on the substrate. Laser irradiation beyond a certain laser power is required to obtain a stoichiometric titanium nitride (TiN) layer. A TiN layer and an oxynitride layer with a TiO_xN_y-like structure are formed as the topmost and the lower surface layer, respectively, when the laser power exceeds this threshold value. The threshold laser power strongly depends on the wavelength of the laser, and this threshold value for the 532-nm laser is quite lower than that for the 1064-nm laser.     

Pure and Nb-doped TiO1.5 films grown by pulsed-laser deposition for transparent p-n homojunctions

Pure and Nb-doped titanium oxide thin films were grown on sapphire substrates by pulsed-laser deposition in vacuum (10⁻⁷ mbar). The PLD growth leads to titanium oxide thin films displaying a high oxygen deficiency (TiO_1.5) compared with the stoichiometric TiO₂ compound. The structural and electrical properties (phase, crystalline orientation, nature and concentration of charge carriers, etc.) of these titanium oxide films were studied by XRD measurements and Hall effect experiments, respectively. The undoped TiO_1.5 phase displayed a p-type semiconductivity. Doping this titanium oxide phase with Nb⁵⁺ leads to an n-type behaviour as is generally observed for titanium oxide films with oxygen deficiency (TiO_x with 1.7 < x < 2). Multilayer homojunctions were obtained by the stacking of TiO_1.5 (p-type) and Nb-TiO_1.5 (n-type) thin films deposited onto sapphire substrates. Each layer is 75 nm thick and the resulting heterostructure shows a good transparency in the visible range. Finally, the I-V curves obtained for such systems exhibit a rectifying response and demonstrate that it is possible to fabricate p-n homojunctions based only on transparent conductive oxide thin films and on a single chemical compound (TiO_x).     

Effect of nano-titanium hydride on formation of multi-nanoporous TiO2 film on Ti

The effect of titanium hydride on the formation of nanoporous TiO₂ on Ti during anodization has been investigated by X-ray photoelectron spectroscopy, grazing incident X-ray diffraction, transmission electron microscopy and scanning electron microscopy. Titanium hydride (TiH₂) was formed after cathodization, profoundly impacting the formation of nanoporous TiO₂ on Ti by anodization. Oxide layer and nanocrystal structure were observed after anodization with cathodic pretreatments. A multi-nanoporous TiO₂ layer was formed on the titanium. The titanium hydride is a nanostructure. The nanostructure is directly changed to nanoporous TiO₂ by a dissolution reaction during anodization. The nanoporous layer is difficult to form without cathodization. The nanostructural TiH₂ is important in forming a nanoporous TiO₂ layer. Anodization treatment with cathodic pretreatment not only yields a titanium surface with a multi-nanostructure, but also transforms the titanium surface into a nanostructured titanium oxide surface.     

Effect of manganese ions concentration on the anatase–rutile phase transformation of TiO2 films

The phase structures of Ti_1?xMn_xO₂ (0?x<0.08) films synthesized by sol–gel spin coating have been investigated. The effect of Mn dopants on the stability of titanium dioxide (TiO₂) was studied by X-ray diffraction and Raman spectra for isochronally annealed samples. The increased Mn dopant concentration decreased the onset temperature of anatase–rutile (A–R) phase transformation. The calculated activation energy for the phase transformation decreased from 173.6 to 89.4 kJ/mol with Mn dopants concentration increasing from 0% to 7.51%. The Mn ions incorporated into the TiO₂ lattice reduce the rutile nucleation barrier and promote the nucleation rate.     

The improvement of pyroelectric properties of PZT thick films on Si substrate by TiOx barrier layer

The effects of TiO_x diffusion barrier layer thickness on the microstructure and pyroelectric characteristics of PZT thick films were studied in this paper. The TiO_x layer was prepared by thermal oxidation of Ti thin film in air and the PZT thick films were fabricated by electrophoresis deposition method (EPD). To demonstrate the barrier effect of TiO_x layer, the electrode/substrate interface and Si content in PZT thick films were characterized by scanning electron microscope (SEM) and X-ray energy dispersive spectroscopy (EDS), respectively. The TiO_x barrier thickness shows significant influence on the bottom electrode and the pyroelectric performance of the PZT thick films. The average pyroelectric coefficient of PZT films deposited on 400 nm TiO_x layer was about 8.94 × 10⁻⁹ C/(cm² K), which was improved by 70% than those without diffusion barrier layer. The results showed in this study indicate that TiO_x barrier layer has great potential in fabrication of PZT pyroelectric device.     

Surface functionalisation of polymer nanofibres by sputter coating of titanium dioxide

The surface properties of nanofibres are of importance in various applications. In this work, electrospun polyamide nanofibres were used as substrates for creating functional nanostructures on the nanofibre surfaces. A RF magnetron sputter coating was used to deposit the functional layer of titanium dioxide (TiO₂) onto the nanofibres. Atomic force microscopy (AFM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and environmental scanning electron microscopy (ESEM) were employed to study the topography, grain structure and wetting of the nanofibre surfaces, respectively. The AFM results indicated a significant difference in the morphology of the nanofibres before and after the TiO₂ sputter coating. The XRD analysis showed the amorphous structures of the TiO₂ deposition layer. XPS spectra reflected the chemical features of the deposited nanostructures. The ESEM observation revealed that the surface wettability of TiO₂ sputter coated nanofibres was significantly improved after UV irradiation.     

Crystalline TiO2 grafted with poly(2-methacryloyloxyethyl phosphorylcholine) via surface-initiated atom-transfer radical polymerization

Crystalline TiO₂ films were prepared by unbalanced magnetron sputtering and the structure was confirmed by XRD. An organic layer of 11-hydroxyundecylphosphonic acid (HUPA) was prepared on the TiO₂ films by self-assembling, and the HUPA on TiO₂ films was confirmed by FTIR analysis. Simultaneously, hydroxyl groups were introduced in the phosphonic acid molecules to provide a functionality for further chemical modification. 2-Methacryloyloxyethyl phosphorylcholine (MPC), a biomimetic monomer, was chemically grafted on the HUPA surfaces at room temperature by surface-initiated atom-transfer radical polymerization. The surface characters of TiO₂ films modified by poly-MPC were confirmed by FTIR, XPS and SEM analysis. Platelet adhesion experiment revealed that poly-MPC modified surface was effective to inhibit platelet adhesion in vitro.     

Characterization of ceramic PVD thin films on AZ31 magnesium alloys

Ceramic thin films have been widely used to protect the metal substrate as coatings in the past years. In order to improve the poor corrosion resistance of AZ31 magnesium alloy, the study in this paper used the electron beam evaporation method to prepare ceramic PVD films on its surface with TiO₂ and Al₂O₃ as donors, respectively. Atomic force microscopy (AFM), scanning electron microscope (SEM), energy dispersive X-ray spectrometer (EDS), Auger electron spectroscopy (AES) and X-ray diffraction (XRD) were used to investigate the surface morphology, composition and microstructure of the thin films. Both films deposited on AZ31 took on compact top surface morphologies and grew as amorphous structures on substrate. AES test not only showed that films compositions deviated the standard stoichiometric ratios, but also found that element Mg diffused into films and existed as magnesium oxide in the TiO_x film as well as the AlO_x film. In the electrochemical corrosion test, the AlO_x coating on AZ31 exhibited the largest electrochemical impedance in a 3.5% NaCl solution. But it did not show better corrosion resistance than others for the poorer adhesion. Even if its thickness was small, the TiO_x coating on AZ31 exhibited the best corrosion resistance in this study. According to the observation and analysis, the damage of these films on AZ31 in aggressive solutions was mainly due to the existence of pores, microcracks, vacancies and poor adhesion between coating and substrate.     

Optimal levels of oxygen deficiency in the visible light photocatalyst TiO2−x and long-term stability of catalytic performance

The dependence of the visible light-responsive photocatalytic activity of oxygen deficient TiO₂ (TiO_2−x) prepared by Ar/H₂ plasma surface treatment on the degree of oxygen deficiency (x) was assessed to determine the deficiency region associated with highest performance. The highest activity was obtained at x=0.06 (TiO_1.94). The maximum visible light activity for this material, estimated from the formaldehyde (HCHO) removal rate, was three times higher than that exhibited by nitrogen-doped TiO₂ (TiO_2−xN_x). The catalytic ability was found to decrease over the first week after fabrication of the material, after which it became stable, and the performance of TiO_2−x at this point was found to be nearly equal to that of TiO_2−xN_x. The results of ab initio calculations of density of states for TiO_2−x suggest that new oxygen deficiency states emerge at almost the exact center between the valence and conduction bands when x>0.06, which increases the recombination rate between electrons and holes. Therefore the declining performance of TiO_2−x at larger x values is attributed to the emergence of new oxygen deficient states.     

The preparation of nitrogen-doped TiO2−xNx photocatalyst coated on hollow glass microbeads

In this paper, the effective method for nitrogen-doped TiO_2−xN_x photocatalyst coated on hollow glass microbeads is described, which uses titanium tetraisopropoxide [Ti(iso-OC₃H₇)₄] as the raw materials and gaseous ammonia as a heat treatment atmosphere. The effects of heat treatment temperature and time on the photocatalytic activity of TiO_2−xN_x/beads are studied. The photocatalyst is characterized by the UV-vis diffuse reflection spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), Brunauer-Emmett-Teller (BET) analysis and scanning electron microscopy (SEM). The results show that when the TiO_2−xN_x/beads is heated at 650 °C for 5 h, the photocatalytic activity of the TiO_2−xN_x/beads is the best. Compared with TiO₂, the photoabsorption wavelength range of nitrogen-doped TiO_2−xN_x red shifts of about 60 nm, and the photoabsorption intensity increases as well. The photocatalytic activity of the TiO_2−xN_x/beads is higher than that of the TiO₂/beads under visible light irradiation. The presence of nitrogen neither influences on the transformation of anatase to rutile, nor creates new crystal phases. When the TiO_2−xN_x/beads is heated at 650 °C for 5 h, the amount of nitrogen-doped is 0.53 wt.% in the TiO_2−xN_x. As the density of TiO_2−xN_x/beads prepared is lower than 1.0 g/cm³, it may float on water surface and use broader sunlight spectrum directly.     

Compositional dependence of in-vitro bioactivity in sodium calcium borate glasses

Borate glasses with composition xCaO (100−x) B₂O₃ (20≤x≤50), where x is in mole percent) and 50CaO·45B₂O₃·5Na₂O have been prepared using conventional melt quench technique. Samples were submerged in simulating body fluid solution (SBF) at 37 °C for various periods of time. After storage the samples were analyzed in order to investigate if a surface layer of hydroxyl carbonate apatite layer (HCA layer/Ca-P layer) had formed. The analysis technique used included Fourier-Transform Infrared Spectroscopy (FTIR). The rate of HCA layer formation on the surface of exposed glass samples is determined by FTIR, percentage weight loss measurements of glass samples in SBF and variation of pH of SBF as a function of time. Increase in calcium content in the glass matrix has shown to decrease the rate of HCA formation on glass surfaces. The borate glass with x=20 has shown HCA layer formation on glass surface within two days of dipping. The bone like apatite formation of glass surface demonstrates the potential of glass for integration with bone.     

Low-temperature biomimetic formation of apatite/TiO2 composite coatings on Ti and NiTi shape memory alloy and their characterization

Through a low temperature process, a bilayer composite coating was formed on Ti and NiTi shape memory alloy (SMA). The composite coating consisted of a layer of titania, which was formed using a H₂O₂-oxidation and hot water aging technique, and a layer of apatite, which was formed through an accelerated biomimetic process by immersing as-oxidized metals in a high-strength simulated body fluid (5SBF). Various techniques including X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy were used to characterize the surfaces of samples at different stages of coating formation and the coatings formed. Bioactive apatite/TiO₂ coatings could be formed on NiTi SMA and firmly bonded to the metal substrate. But there were differences for the formation of the composite coating on Ti and NiTi SMA substrates. The composite coatings formed will render both metals bioactive and hence bone-bonding.     

Mechanical performance of apatite/TiO2 composite coatings formed on Ti and NiTi shape memory alloy

To make metals bioactive for orthopaedic applications, apatite/TiO₂ composite coatings were formed on Ti and NiTi shape memory alloy (SMA) using a H₂O₂-oxidation and hot water aging technique and the subsequent accelerated biomimetic process. In the current investigation, nanoindentation, scratch testing and frictional testing were employed to assess mechanical properties and the adhesion of apatite/TiO₂ composite coatings formed on Ti and NiTi SMA. Nanoindentation testing conducted on cross-sections of composite coatings indicated that there was no significant difference in nanohardness and elastic modulus between apatite/TiO₂ composite coatings formed on Ti and NiTi SMA samples. The enhancement of the adhesion between the apatite layer and the metal substrates arose from the TiO₂ intermediate layer in the composite coating. The highest values of coating adhesion strength for Ti and NiTi SMA samples, as measured by scratch tests, were 22.58 N and 19.07 N, respectively. However, compared to corresponding Ti samples, NiTi SMA samples had better tribological properties.     

Influence of deposition atmosphere on photocatalytic activity of TiO2/SiOx double-layers prepared by RF magnetron sputtering

TiO₂/SiO_x double-layers have been prepared at room temperature by RF magnetron sputtering. The TiO₂ top-layer was deposited in an Ar atmosphere, while the SiO_x bottom-layer was deposited in an Ar/O₂ atmosphere. Samples were characterized using X-ray photoelectron spectroscopy, scanning electron microscopy, atomic force microscopy, and photoluminescence techniques. The photocatalytic activity of the samples was evaluated by the photodegradation of methylene blue; the results showed that the photocatalytic activity of the TiO₂/SiO_x double-layers was superior to that of the TiO₂ single-layers. The presence of the SiO_x bottom-layer improved the photocatalytic activity of the TiO₂ layer because it may act as a trap for electrons generated in the TiO₂ layer thus preventing electron-hole recombinations.     

Reaction products and oxide thickness formed by Ti out-diffusion and oxidization in poly-Pt/Ti/SiO2/Si with oxide films deposited

In the paper, we present experimental results to enhance the understanding of Ti out-diffusion and oxidization in commercial poly-Pt/Ti/SiO₂/Si wafers with perovskite oxide films deposited when heat-treated in flowing oxygen ambient. It indicates that when heat-treated at 550 and 600 °C, PtTi₃+PtTi and PtTi are the reaction products from interfacial interaction, respectively; while heat-treated at 650 °C and above, the products become three layers of titanium oxides instead of the alloys. Confirmed to be rutile TiO₂, the first two layers spaced by 65 nm encapsulate the Pt surface by the first layer with 60 nm thick forming at its surface and by the next layer with 35 nm thick inserting its original layer. In addition, the next layer is formed as a barrier to block up continuous diffusion paths of Ti, and thus results in the last layer of TiO_2−x formed by the residual Ti oxidizing.     

Activation energy of hydrogen desorption from high-performance titanium oxide carrier-selective contacts with silicon oxide interlayers

The impact of hydrogen desorption on the electrical properties of TiO_x on crystalline silicon (c-Si) with SiO_y interlayers is studied for the development of high-performance TiO_x carrier-selective contacts. Compared with the TiO_x/c-Si heterocontacts, a lower surface recombination velocity of 9.6 cm/s and lower contact resistivity of 7.1 mΩ cm² are obtained by using SiO_y interlayers formed by mixture (often called SC2). The hydrogen desorption peaks arising from silicon dihydride (α1) and silicon monohydride (α2) on the c-Si surface of the as-deposited samples are observed. The α1 peak pressure of as-deposited heterocontacts with SiO_x interlayers is lower than that of heterocontacts without a SiO_y interlayer. Furthermore, the hydrogen desorption energies are found to be 1.76 and 2.13 eV for the TiO_x/c-Si and TiO_x/SC2-SiO_y/c-Si heterocontacts, respectively. Therefore, the excellent passivation of the TiO_x/SC2-SiO_y/c-Si heterocontacts is ascribed to the relatively high rupture energy of bonding between Si and H atoms.     

Titanium dioxide-coated nanofibers for advanced filters

This article reports on titanium dioxide (TiO₂)-coated nanofibers deposited on a filter surface by the electrospinning process. After depositing a micrometer-thick film of polyamide 11 nanofibers on polypropylene fabric, TiO₂ nanoparticles can be directly electrosprayed onto the nanofibers. X-ray diffraction and Raman spectroscopy showed minimal change in the phase composition (anatase and rutile) and no change in the particle size of nanocrystalline TiO₂ after coating. Scanning electron microscopy demonstrated that nanofibers were uniformly coated by titanium dioxide nanoparticles without agglomeration. TiO₂-coated filters showed excellent photocatalytic-bactericidal activity and photo-induced hydrophilicity.     

Visible-light photocatalytic activity of nitrogen-doped TiO2 thin film prepared by pulsed laser deposition

Nitrogen-doped titanium dioxide (TiO_2−xN_x) thin films have been prepared by pulse laser deposition on quartz glass substrates by ablated titanium dioxide (rutile) target in nitrogen atmosphere. The x value (nitrogen concentration) is 0.567 as determined by X-ray photoelectron spectroscopy measurements. UV-vis spectroscopy measurements revealed two characteristic deep levels located at 1.0 and 2.5 eV below the conduction band. The 1.0 eV level is attributable to the O vacancy state and the 2.5 eV level is introduced by N doping, which contributes to narrowing the band-gap by mixing with the O2p valence band. The enhanced degradation efficiency in a broad visible-light range was observed from the degradation of methylene blue and methylene orange by the TiO_2−xN_x film.