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.     

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.     

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.     

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.     

Low-temperature preparation of F-doped TiO2 film and its photocatalytic activity under solar light

A novel and simple method for preparing F-doped anatase TiO₂ (defined as FTO) film with high photocatalytic activity was developed using titanium-n-butoxide and NH₄F as TiO₂ and fluorine precursors under mild condition, i.e. low temperature (lower than 373 K) and ambient pressure. The prepared samples were characterized by XRD, SEM, X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectrum (DRS), photoluminescence spectrum (PL) and TG-DSC analysis. The photocatalytic activity was evaluated by decomposing X-3B under artificial solar light. The results showed that the crystallinity of TiO₂ was improved by F-doping. F⁻ ions can prevent the grain growth, and the transformation of anatase to rutile phase was also inhibited. The doped fluorine atoms existed in two chemical forms, and the ones incorporated into TiO₂ lattice might take a positive role in photocatalysis. Compared with surface fluorination samples, FTO film exhibited better photocatalytic activity. The high photocatalytic activity of FTO may due to extrinsic absorption through the creation of oxygen vacancies rather than the excitation of the intrinsic absorption band of bulk TiO₂. Furthermore, the FTO can be recycled with little photocatalytic activity depression. Without any further treatment besides rinsing, after 6 recycle utilization, the photocatalytic activity of FTO film was still higher than 79%.     

Optical characterization of PLD grown nitrogen-doped TiO2 thin films

Nitrogen-doped TiO₂ thin films were prepared by pulsed laser deposition (PLD) by ablating metallic Ti target with pulses of 248 nm wavelength in reactive atmospheres of O₂/N₂ gas mixtures. The layers were characterized by UV-VIS spectrophotometry and variable angle spectroscopic ellipsometry with complementary profilometry for measuring the thickness of the films. Band gap and extinction coefficient values are presented for films deposited at different substrate temperatures and for varied N₂ content of the gas mixture. The shown tendencies are correlated to nitrogen incorporation into the TiO_2-xN_x layers. It is shown that layers of significantly increased visible extinction coefficient with band gap energy as low as 2.89 eV can be obtained. A method is also presented how the spectroscopic ellipsometric data should be evaluated in order to result reliable band gap values.     

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.     

Low-temperature transport properties of individual SnO2 nanowires

Stannic oxide (SnO₂) nanowires have been prepared by Chemical vapor deposition (CVD). The low-temperature transport properties of a single SnO₂ nanowire have been studied. It is found that the transport of the electrons in the nanowires is dominated by the Efros-Shklovskii variable-range hopping (ES-VRH) process due to the enhanced Coulomb interaction in this semiconducting nanowire. The temperature dependence of the resistance follows the relation lnR∼T^−1/2. On the I-V and dI/dV curves of the nanowire a Coulomb gap-like structure at low temperatures appears.     

Fabrication and characterization of facing-target reactive sputtered polycrystalline TiO2 films

Polycrystalline TiO₂ films were fabricated using dc facing-target reactive sputtering at different sputtering pressures. The films deposited consist of pure anatase phase or a mixture of anatase and rutile and increasing rutile content to some extent deteriorates the crystallinity of the anatase. It was found that the plasma heating effect, which plays the role of substrate heating, is an important factor for the crystallinity of the films in the case of without substrate heating. The roughness of the films increases monotonically with the increase of the sputtering pressure, which can be ascribed to the decrease in the mobility of the impinging particles. UV-vis transmission measurements reveal that the pure anatase films have higher transmittance than those having mixed phases of anatase and rutile. The band gap value decreases from ∼3.35 to 3.29 eV owing to the increase in the fraction of rutile phase.     

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.     

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.     

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.     

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.     

Structural and morphological characterization of TiO2 nanostructured films grown by nanosecond pulsed laser deposition

TiO₂ has attracted a lot of attention due to its photocatalytic properties and its potential applications in environmental purification and self cleaning coatings, as well as for its high optical transmittance in the visible-IR spectral range, high chemical stability and mechanical resistance. In this paper, we report on the growth of TiO₂ nanocrystalline films on Si (1 0 0) substrates by pulsed laser deposition (PLD). Rutile sintered targets were irradiated by KrF excimer laser (λ = 248 nm, pulse duration ∼30 ns) in a controlled oxygen environment and at constant substrate temperature of 650 °C. The structural and morphological properties of the films have been studied for different deposition parameters, such as oxygen partial pressure (0.05-5 Pa) and laser fluence (2- 4 J/cm²). X-ray diffraction (XRD) shows the formation of both rutile and anatase phases; however, it is observed that the anatase phase is suppressed at the highest laser fluences. X-ray photoelectron spectroscopy (XPS) measurements were performed to determine the stoichiometry of the grown films. The surface morphology of the deposits, studied by scanning electron (SEM) and atomic force (AFM) microscopies, has revealed nanostructured films. The dimensions and density of the nanoparticles observed at the surface depend on the partial pressure of oxygen during growth. The smallest particles of about 40 nm diameter were obtained for the highest pressures of inlet gas.     

Low-temperature thermoluminescence in CaGa2S4:Eu

In the last years many insulating and semiconducting materials activated with rare-earth elements were found to exhibit phosphorescence and thermoluminescence properties, and are attracting increasing interest due to the variety of application of long-lasting phosphors. In this work we studied the phosphorescence decay and thermoluminescence properties of CaGa₂S₄:Eu²⁺ as a function of temperature in the 9-325 K range. The comparison between spectra recorded as a function of time delay from the excitation pulse at different temperatures indicates that long-lasting emissions peaked at about 2.2 eV occurs at Eu²⁺ sites. Thermoluminescence glow curve is characterized by five components at 69, 98, 145, 185 and 244 K. Experimental data are discussed in the framework of generalized order of kinetic model and allow to estimate the activation energies of trapping defects. The origin of glow components at 69, 98, 145 and 244 K is correlated to trapping defects induced by Eu²⁺ doping, while the component at 185 K is attributed to a continuous distribution of defects.