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.     

Pulsed laser deposition of hydroxyapatite film on laser gas nitriding NiTi substrate

A hydroxyapatite (HA) film was deposited on laser gas nitriding (LGN) NiTi alloy substrate using pulsed laser deposition technique. TiN dendrite prepared by LGN provided a higher number of nucleation sites for HA film deposition, which resulted in that a lot number of HA particles were deposited on TiN dendrites. Moreover, the rough LGN surface could make the interface adhesive strength between HA film and substrate increase as compared with that on bare NiTi substrate.     

Preparation and photocatalytic activity of CeO2/TiO2 interface composite film

The CeO₂/TiO₂ and TiO₂/CeO₂ interface composite films were prepared on glass substrates by the sol-gel process via dip-coating and calcining technique. The scanning electron microscopy (SEM) revealed that the TiO₂ layer has a compact and uniformity glasslike surface with 200 nm in thickness, and the CeO₂ layer has a coarse surface with 240 nm in thickness. The X-ray diffractometer (XRD) analysis showed that the TiO₂ layer is made up of anatase phase, and the CeO₂ layer is structured by cubic fluorite phase. Through a series of photo-degradation experiments, the relationship of the photocatalytic activity with the constituents of the films was studied. In virtue of the efficient interfacial charge separation via the process of electron transfer from TiO₂ to CeO₂, the photocatalytic activity of the CeO₂/TiO₂ composite film is high. Contrarily, the photocatalytic activity of the TiO₂/CeO₂ composite film is low, due to its inert surface made up of CeO₂ with broad bandwidth. Apart from the effect of the film structure, the effect of film thickness on photocatalytic activity was also discussed.     

Ni-doped TiO2 nanotube arrays on shape memory alloy

Self-organized Ni-Ti-O nanotube arrays were fabricated through a direct anodization of NiTi shape memory alloy in glycerol-based electrolyte. The growth of Ni-doped TiO₂ nanotube arrays was mainly affected by anodization voltage and temperature. Higher anodization voltage facilitated the growth of uniform nanotube arrays. Large-area open-ended Ni-Ti-O nanotube arrays could form on the surface of the shape memory alloy under a higher anodization temperature. The oxide nanotubes had a gradually changed composition along the growth direction of the nanotube and presented a thermal stability up to 400 °C. The nanotubular oxide demonstrated a much better hydrophilic behavior than that of the traditional oxide layer grown on NiTi substrate through air oxidization. The successful fabrication of Ni-doped TiO₂ nanotube arrays here makes it feasible to further explore excellent physical and chemical as well as biomedical properties of the nanotube-modified surfaces of the NiTi shape memory alloy.     

Deposition of Ag nanostructures on TiO2 thin films by RF magnetron sputtering

Ag nanostructures on TiO₂ films were deposited by RF magnetron sputtering under variable deposition parameters, such as DC potential, RF-power and total pressure. The concentration, shape, and distribution of the deposited nanostructures and continuous Ag films on thin films of TiO₂ can be tailored by careful variation of the deposition parameters. Controllable clusterlike, islandlike and film Ag structures on TiO₂ film were obtained, respectively. DC potential was found as an appropriate parameter to tailor the change of Ag nanostructure and the overall Ag amount. The compositions, nanostructures and morphologies of nanocomposite films appreciably influence the optical response.     

Effect of fluoride-ion implantation on the biocompatibility of titanium for dental applications

This study stressed on the effect of fluoride-ion implantation upon the biocompatibility of titanium. By using plasma immersion ion implantation technique, fluoride ions were implanted into the smooth surface of pure titanium. The chemical composition and physical structure of the modified surface layers were characterized by X-ray photoelectron spectroscopy (XPS) as well as scanning electron microscope (SEM). At the same time, in vitro co-culture assays were performed to evaluate the biocompatibility of MG-63 cells to the modified titanium. It was confirmed by SEM observations that cell growth on the fluoride-ion-implanted titanium acquired better morphological characters. In addition, the cells on the fluoride-ion-implanted titanium showed the more increasingly and rapidly substrates-attaching capabilities than those on the non-implanted titanium via aridine orange stain assay. Fluoride-ion-implanted titanium could increase the percentages of cells in S phase but without affecting the ratios of cells in G₀/G₁ and G₂/M phases was confirmed by flow cytometry assay. The current results indicated that fluoride-ion implantation could improve the biocompatibility of titanium.     

Influence of zinc ion implantation on surface nanomechanical performance and corrosion resistance of biomedical magnesium-calcium alloys

It is believed that magnesium and its alloys may find applications in biomedical fields as implants, bone fixation devices, and tissue engineering scaffolds. However, their corrosion rate must be controlled. In this study, biomedical magnesium-calcium (Mg-Ca) alloys were ion-implanted with zinc. The surface nanomechanical performance and corrosion behavior of the ion-implanted Mg-Ca alloys are determined. The results show that zinc ion implantation at a dose of 0.9 × 10¹⁷ ions/cm² significantly improves the surface hardness and modulus. However, the results on corrosion resistance reveal that zinc ion implantation degrades the corrosion behavior of Mg-Ca alloys. Thus, zinc is not a favorable element for the ion implantation treatment of biomedical Mg-Ca alloys.     

Electrical transport and thermal properties of ferromagnetic shape memory alloy Ni49.4Mn30Ga20.6

The electrical transport and thermal properties of the ferromagnetic shape memory alloy Ni_49.4Mn₃₀Ga_20.6 are measured. Near around the starting point from austenite to martensite transition, the temperature (T) dependence of resistance for the sample shows a clear jump due to a great scattering mechanism introduced by the transformation resulting in many interfaces during the process. T-dependent curve of the thermoelectric power (S) of the sample shows linear dependence below martensitic transformation temperature with its absolute value decreasing during cooling. The absolute value of S   tends to reach at a maximum at the martensitic transformation which is reflected by ∂S/∂T$\mathrm{\partial }S/\mathrm{\partial }\mathrm{T}$∼0. This may be related to the changes of the density of states near the phase transformation and the corresponding scattering introduced.     

Effect of NaAlO2 concentrations on microstructure and corrosion resistance of Al2O3/ZrO2 coatings formed on zirconium by micro-arc oxidation

In this study, Al₂O₃/ZrO₂ composite coatings were prepared on Zr substrates by micro-arc oxidation (MAO) in the NaAlO₂-containing electrolytes, and the effect of NaAlO₂ concentration on the microstructure, bond strength, microhardness and corrosion resistance of coatings was systematically investigated. The study reveals that the adequate NaAlO₂ in the electrolyte (>0.2 M) is essential to the formation of needle-like α-Al₂O₃ in the coatings, and the amount of α-Al₂O₃ rises with the increase of the NaAlO₂ concentration. m-ZrO₂ and t-ZrO₂ are present in all of the coatings, but their relative amount largely depends on the amount of Al₂O₃. It is also found that as the NaAlO₂ concentration increases from 0.2 to 0.3 M, the coating becomes denser and thicker, and its bond strength, maximum microhardness and corrosion resistance increases as well. The coating formed at 0.3 M NaAlO₂ demonstrates the highest bond strength of 52 MPa, the maximum microhardness of 1600 Hv_0.2N and the superior corrosion resistance. However, the overhigh concentration of NaAlO₂ (0.35 M) is found harmful to the coating's microstructure and properties.     

Surface XPS characterization of NiTi shape memory alloy after advanced oxidation processes in UV/H2O2 photocatalytic system

Surface structure of NiTi shape memory alloy (SMA) was modified by advanced oxidation processes (AOP) in an ultraviolet (UV)/H₂O₂ photocatalytic system, and then systematically characterized with x-ray photoelectron spectroscopy (XPS). It is found that the AOP in UV/H₂O₂ photocatalytic system leads to formation of titanium oxides film on NiTi substrate. Depth profiles of O, Ni and Ti show such a film possesses a graded interface structure to NiTi substrate and there is no intermediate Ni-rich layer like that produced in conventional high temperature oxidation. Except TiO₂ phase, some titanium suboxides (TiO, Ti₂O₃) may also exist in the titanium oxides film. Oxygen mainly presents in metal oxides and some chemisorbed water and OH⁻ are found in titanium oxides film. Ni nearly reaches zero on the upper surface and relatively depleted in the whole titanium oxides film. The work indicates the AOP in UV/H₂O₂ photocatalytic system is a promising way to favor the widespread application of biomedical NiTi SMA by improving its biocompatibility.     

Preparation and characterization of poly(lactic acid)-grafted TiO2 nanoparticles with improved dispersions

Poly(lactic acid) (PLA)-grafted TiO₂ particles were prepared by in situ melt polycondensation of lactic acid onto the surface of TiO₂ nanoparticles. The resulting products were characterized by FTIR, XPS, TG-FTIR, XRD analysis and electron microscopy observation so as to have a better understanding of bonding between the graft polymer and nanoparticles. New characteristic peaks of Ti-carboxylic coordination bond, the changes in the relative intensities of the infrared absorption bands of graft polymer and the two decomposition stage of PLA-grafted TiO₂ confirmed that PLA was grafted on the surface of TiO₂ nanoparticles. By attachment of PLA, the PLA-grafted TiO₂ samples exhibited much better dispersion and a slightly larger particle size than bare TiO₂ particles. PLA-grafted TiO₂ nanoparticles will find wide applications in biomedical and eco-friendly materials, especially as fillers in PLA matrix.     

Electrodeposition and properties of Zn-nanosized TiO2 composite coatings

Nanosized TiO₂ particles were prepared by sol-gel method. The TiO₂ particles were co-deposited with zinc from a sulphate bath at pH 4.5 using electrodeposition technique. The corrosion behavior of the coatings was assessed by electrochemical polarization, impedance, weight-loss and salt spray tests. Wear resistance and microhardness of the composite coating was measured. The smaller grain size of the composite coatings was observed in the presence of TiO₂ and it was confirmed by the images of scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques.     

Selective cell culture on UV transparent polymer by F2 laser surface modification

A microchip made of UV transparent polymer (CYTOP) that can perform selective cell culture has been fabricated by F₂ laser surface modification. The refractive index of CYTOP is almost the same as that of culture medium, which is essential for three-dimensional (3D) observation of cells. The F₂ laser modification of CYTOP achieves hydrophilicity only on the laser irradiated area with little deterioration of the optical properties and surface smoothness. After the laser modification, HeLa cells were successfully cultured and strongly adhered only on the modified area of CYTOP. The cells patterned on CYTOP were applied for clear 3D observation using an optical microscope in phase contrast mode.     

Investigation of thin TiO2 films cosputtered with Si species

Titanium dioxide (TiO₂) films were fabricated by cosputtering titanium (Ti) target and SiO₂ or Si slice with ion-beam-sputtering deposition (IBSD) technique and were postannealed at 450 °C for 6 h. The variations of oxygen bonding, which included high-binding-energy oxygen (HBO), bridging oxygen (BO), low-binding-energy oxygen (LBO), and three chemical states of titanium (Ti⁴⁺, Ti³⁺ and Ti²⁺) were analyzed by X-ray photoelectron spectroscopy (XPS). The enhancement of HBO and reduction of BO in O 1s spectra as functions of SiO₂ or Si amount in cosputtered film imply the formation of Si-O-Ti linkage. Corresponding increase of Ti³⁺ in Ti 2p spectra further confirmed the property modification of the cosputtered film resulting from the variation of the chemical bonding. An observed correlation between the chemical structure and optical properties, refractive index and extinction coefficient, of the SiO₂ or Si cosputtered films demonstrated that the change of chemical bonding in the film results in the modification of optical properties. Furthermore, it was found that the optical properties of the cosputtered films were strongly depended on the cosputtering targets. In case of the Si cosputtered films both the refractive indices and extinction coefficients were reduced after postannealing, however, the opposite trend was observed in SiO₂ cosputtered films.     

Effects of rapid thermal annealing on the structural properties of TiO2 nanotubes

The structural properties of TiO₂ nanotubes with rapid thermal annealing (RTA) and traditional thermal annealing in O₂ were studied by X-ray diffraction (XRD) and Raman scattering measurements. From analyzing the line width of XRD and the correlation length of the Raman peak, we demonstrate that RTA can be an effective tool for amorphous-anatase transformation in TiO₂ nanotubes. The Raman peak redshifts and reduces its line width after thermal annealing and RTA, which may involves the reduction of oxygen-related defects.     

Structure, magnetic and optical properties of polycrystalline Co-doped TiO2 films

Co-doped TiO₂ films were fabricated under different conditions using reactive facing-target magnetron sputtering. Co doping improves the transformation of TiO₂ from anatase phase to rutile phase. The chemical valence of doped Co in the films is +2. All the films are ferromagnetic with a Curie temperature above 340 K. The average room-temperature moment per Co of the Co-doped TiO₂ films fabricated at 1.86 Pa decreases from 0.74 μ_B at x=0.03 to 0.02 μ_B at x=0.312, and decreases from 0.54 to 0.04 μ_B as x increases from 0.026 to 0.169 for the Co-doped TiO₂ films fabricated at 0.27 Pa. The ferromagnetism originates from the oxygen vacancies created by Co²⁺ dopants at Ti⁴⁺ cations. The optical band gaps value (E_g) of the Co-doped TiO₂ films fabricated at 1.86 Pa decreases linearly from 3.35 to 2.62 eV with the increasing x from 0 to 0.312. For the Co-doped TiO₂ films fabricated at 1.86 Pa, the E_g decreases linearly from 3.26 to 2.53 eV with increasing x from 0 to 0.350.     

Microstructure and dielectric properties of (Ba0.6Sr0.4)TiO3 thin films grown on super smooth glazed-Al2O3 ceramics substrate

Modified substrates with nanometer scale smooth surface were obtained via coating a layer of CaO-Al₂O₃-SiO₂ (CaAlSi) high temperature glaze with proper additives on the rough-95% Al₂O₃ ceramics substrates. (Ba_0.6Sr_0.4)TiO₃ (BST) thin films were deposited on modified Al₂O₃ substrates by radio-frequency magnetron sputtering. The microstructure, dielectric, and insulating properties of BST thin films grown on glazed-Al₂O₃ substrates were investigated by X-ray diffraction (XRD), atomic force microscope (AFM), and dielectric properties measurement. These results showed that microstructure and dielectric properties of BST thin films grown on glazed-Al₂O₃ substrates were almost consistent with that of BST thin films grown on LaAlO₃ (1 0 0) single-crystal substrates. Thus, the expensive single-crystal substrates may be substituted by extremely cheap glazed-Al₂O₃ substrates.     

The optical absorption edge of brookite TiO2

The optical absorption edge of brookite TiO₂ was measured at room temperature, using natural crystals. The measurements extend up to 3.54 eV in photon energy and 2000 cm⁻¹ in absorption coefficient. The observed absorption edge is broad and extends throughout the visible, quite different from the steep edges of rutile and anatase. No evidence of a direct gap is seen in the range measured. The spectral dependence of the absorption strongly suggests that the brookite form of TiO₂ is an indirect-gap semiconductor with a bandgap of about 1.9 eV.     

Mechanical properties of bulk and nanoscale TiO2 phases

The mechanical properties of bulk and nanoscale TiO₂ phases are examined with a view to assess the available bulk modulus and hardness data, and to understand the size-dependent behaviors. The bulk modulus values of thermodynamically stable bulk TiO₂ phases show a general correlation with Ti-O coordination number. As with the cotunnite-structured (OII) phase, it is likely that the seven-coordinated OI and eight-coordinated fluorite forms of TiO₂ are ultrahard substances. Of the nanoscale phases investigated thus far, nanocrystalline anatase displays the strongest size dependence of bulk modulus values, with possible stiffening behavior effected by incipient grain boundary amorphization under pressure. Nanocrystalline rutile and baddeleyite phases do not show appreciable size dependence in their compression behaviors.     

Photoelectron spectroscopy of nanocrystalline anatase TiO2 films

Nanocrystalline TiO₂ (anatase) films were prepared using either colloidal suspensions or a sol-gel route. The electronic structure of these films was analyzed using X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). Apart from pristine films, films containing defects introduced by annealing under ultra-high vacuum conditions or by ion bombardment were investigated. Generally, annealing in the temperature range up to 720 K results in no significant changes in the XPS and UPS spectra as compared to the pristine state, indicating that the amount of defect formation is too low to be observable by these techniques. On the other hand, ion irradiation causes the appearance of distinct defect states; these could be identified in agreement with previous data from photoemission studies on rutile and anatase single crystals. From UPS, a valence-band width of ∼4.6 eV was determined for the nanocrystalline anatase films.