Materials characterization of TiO2 nanotubes decorated by Au nanoparticles for photoelectrochemical applications.

The structural and chemical modification of TiO2 nanotubes (NTs) by the deposition of a well-controlled Au deposit was investigated using a combination of X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), Scanning Transmission Electron Microscopy (STEM), Raman measurements, UV-Vis spectroscopy and photoelectrochemical investigations. The fabrication of the materials focused on two important factors: the deposition of Au nanoparticles (NPs) in UHV (ultra high vacuum) conditions (1-2 × 10-8 mbar) on TiO2 nanotubes (NTs) having a diameter of ∼110 nm, and modifying the electronic interaction between the TiO2 NTs and Au nanoparticles (NPs) with an average diameter of about 5 nm through the synergistic effects of SMSI (Strong Metal Support Interaction) and LSPR (Local Surface Plasmon Resonance). Due to the formation of unique places in the form of "hot spots", the proposed nanostructures proved to be photoactive in the UV-Vis range, where a characteristic gold plasmonic peak was observed at a wavelength of 580 nm. The photocurrent density of Au deposited TiO2 NTs annealed at 650 °C was found to be much greater (14.7 µA cm-2) than the corresponding value (∼0.2 µA cm-2) for nanotubes in the as-received state. The IPCE (incident photon current efficiency) spectral evidence also indicates an enhancement of the photoconversion of TiO2 NTs due to Au NP deposition without any significant change in the band gap energy of the titanium dioxide (E g ∼3.0 eV). This suggests that a plasmon-induced resonant energy transfer (PRET) was the dominant effect responsible for the photoactivity of the obtained materials.

TiO2 Nanotubes with Pt and Pd Nanoparticles as Catalysts for Electro-Oxidation of Formic Acid.

In the present work, the magnetron sputtering technique was used to prepare new catalysts of formic acid electrooxidation based on TiO2 nanotubes decorated with Pt (platinum), Pd (palladium) or Pd + Pt nanoparticles. TiO2 nanotubes (TiO2 NTs) with strictly defined geometry were produced by anodization of Ti foil and Ti mesh in a mixture of glycerol and water with ammonium fluoride electrolyte. The above mentioned catalytically active metal nanoparticles (NPs) were located mainly on the top of the TiO2 NTs, forming 'rings' and agglomerates. A part of metal nanoparticles decorated also TiO2 NTs walls, thus providing sufficient electronic conductivity for electron transportation between the metal nanoparticle rings and Ti current collector. The electrocatalytic activity of the TiO2 NTs/Ti foil, decorated by Pt, Pd and/or Pd + Pt NPs was investigated by cyclic voltammetry (CV) and new Pd/TiO2 NTs/Ti mesh catalyst was additionally tested in a direct formic acid fuel cell (DFAFC). The results so obtained were compared with commercial catalyst-Pd/Vulcan. CV tests have shown for carbon supported catalysts, that the activity of TiO2 NTs decorated with Pd was considerably higher than that one decorated with Pt. Moreover, for TiO2 NTs supported Pd catalyst specific activity (per mg of metal) was higher than that for well dispersed carbon supported commercial catalyst. The tests at DFAFC have revealed also that the maximum of specific power for 0.2 Pd/TiO2 catalyst was 70% higher than that of the commercial one, Pd/Vulcan. Morphological features, and/or peculiarities, as well as surface composition of the resulting catalysts have been studied by scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), and chemical surface analytical methods (X-ray photoelectron spectroscopy-XPS; Auger electron spectroscopy-AES).

Effect of Pt Deposits on TiO2 Electrocatalytic Activity Highlighted by Electron Tomography.

Characterizing materials at small scales presents major challenges in the engineering of nanocomposite materials having a high specific surface area. Here, we show the application of electron tomography to describe the three-dimensional structure of highly ordered TiO2 nanotube arrays modified with Pt nanoparticles. The titanium oxide nanotubes were prepared by the electrochemical anodization of a Ti substrate after which Pt was deposited by magnetron sputtering. Such a composite shows high electrochemical activity that depends on the amount of the metal and the morphological parameters of the microstructure. However, a TiO2 structure modified with metallic nanoparticles has never been visualized in 3D, making it very difficult to understand the relationship between electrocatalytic activity and morphology. In this paper, TiO2 nanotubes of different sizes and different amounts of Pt were analyzed using the electron microscopy technique. Electrocatalytic activity was studied using the cyclic voltammetry (CV) method. For selected samples, electron tomography 3D structure reconstruction was performed to describe their fine microstructure. The highest activity was detected in the sample having bigger nanotubes (25 V) where the porosity of the structure was high and the Pt content was 0.1 mg cm-2. 3D imaging using electron tomography opens up new possibilities in the design of electrocatalytic materials.

An electron microscopy three-dimensional characterization of titania nanotubes.

To characterize complex, three-dimensional nanostructures, modern microscopy techniques are needed, such as electron tomography and focused ion beam (FIB) sectioning. The aim of this study was to apply these two techniques to characterize TiO2 nanotubes in terms of their size, shape, volume, porosity, geometric surface area, and specific surface area (SSA). For these experiments, titania nanotubes were fabricated by means of the electrochemical oxidation of titanium at a voltage of 20 V for 2 hr followed by heat treatment at 450°C for 3 hr to change the amorphous structure into a crystalline anatase structure. The quantitative data obtained from the FIB and electron tomography reconstructions show a high similarity in porosity and some differences in SSA. These might be the result of differences in resolution between the two reconstruction techniques.

Metal TiO2 Nanotube Layers for the Treatment of Dental Implant Infections.

Titanium oxide nanotube layers with silver and zinc nanoparticles are attracting increasing attention in the design of bone and dental implants due to their antimicrobial potential and their ability to control host cell adhesion, growth, and differentiation. However, recent reports indicate that the etiology of dental infections is more complex than has been previously considered. Therefore, the antimicrobial potential of dental implants should be evaluated against at least several different microorganisms cooperating in human mouth colonization. In this study, Ag and Zn nanoparticles incorporated into titanium oxide nanotubular layers were studied with regard to how they affect Candida albicans, Candida parapsilosis, and Streptococcus mutans. Layers of titanium oxide nanotubes with an average diameter of 110 nm were fabricated by electrochemical anodization, annealed at 650 °C, and modified with approx. 5 wt % Ag or Zn nanoparticles. The surfaces were examined with the scanning electron microscopy-energy dispersive X-ray analysis, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy techniques and subjected to evaluation of microbial-killing and microbial adhesion-inhibiting potency. In a 1.5 h long adhesion test, the samples were found more effective toward yeast strains than toward S. mutans. In a release-killing test, the microorganisms were almost completely eliminated by the samples, either within 3 h of contact (for S. mutans) or 24 h of contact (for both yeast strains). Although further improvement is advisable, it seems that Ag and Zn nanoparticles incorporated into TiO2 nanotubular surfaces provide a powerful tool for reducing the incidence of bone implant infections. Their high bidirectional activity (against both Candida species and S. mutans) makes the layers tested particularly promising for the design of dental implants.

WxC-ß-SiC Nanocomposite Catalysts Used in Aqueous Phase Hydrogenation of Furfural.

This study investigates the effects of the addition of tungsten on the structure, phase composition, textural properties and activities of ß-SiC-based catalysts in the aqueous phase hydrogenation of furfural. Carbothermal reduction of SiO2 in the presence of WO3 at 1550 °C in argon resulted in the formation of WxC-ß-SiC nanocomposite powders with significant variations in particle morphology and content of WxC-tipped ß-SiC nano-whiskers, as revealed by TEM and SEM-EDS. The specific surface area (SSA) of the nanocomposite strongly depended on the amount of tungsten and had a notable impact on its catalytic properties for the production of furfuryl alcohol (FA) and tetrahydrofurfuryl alcohol (THFA). Nanocomposite WxC-ß-SiC catalysts with 10 wt % W in the starting mixture had the highest SSA and the smallest WxC crystallites. Some 10 wt % W nanocomposite catalysts demonstrated up to 90% yield of THFA, in particular in the reduction of furfural derived from biomass, although the reproducible performance of such catalysts has yet to be achieved.

Microstructure of Haynes® 282® Superalloy after Vacuum Induction Melting and Investment Casting of Thin-Walled Components.

The aim of this work was to characterize the microstructure of the as-cast Haynes® 282® alloy. Observations and analyses were carried out using techniques such as X-ray diffraction (XRD), light microscopy (LM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray spectroscopy (EDS), wave length dispersive X-ray spectroscopy (WDS), auger electron spectroscopy (AES) and electron energy-loss spectrometry (EELS). The phases identified in the as-cast alloy include: γ (gamma matrix), γ' (matrix strengthening phase), (TiMoCr)C (primary carbide), TiN (primary nitride), σ (sigma-TCP phase), (TiMo)2SC (carbosulphide) and a lamellar constituent consisting of molybdenum and chromium rich secondary carbide phase together with γ phase. Within the dendrites the γ' appears mostly in the form of spherical, nanometric precipitates (74 nm), while coarser (113 nm) cubic γ' precipitates are present in the interdendritic areas. Volume fraction content of the γ' precipitates in the dendrites and interdendritic areas are 9.6% and 8.5%, respectively. Primary nitrides metallic nitrides (MN), are homogeneously dispersed in the as-cast microstructure, while primary carbides metallic carbides (MC), preferentially precipitate in interdendritic areas. Such preference is also observed in the case of globular σ phase. Lamellar constituents characterized as secondary carbides/γ phases were together with (TiMo)2SC phase always observed adjacent to σ phase precipitates. Crystallographic relations were established in-between the MC, σ, secondary carbides and γ/γ' matrix.

Surface characterization of Ca-P/Ag/TiO2 nanotube composite layers on Ti intended for biomedical applications.

The new generation of medical implants made by titanium is functionalized with different coatings to improve their bioactivity and reduce a risk of infection. This article describes how these goals can be achieved via deposition of silver nanoparticles and calcium phosphate coating. TiO(2) nanotubes were grown on a Ti substrate via electrochemical oxidation at constant voltage in a mixture of glycerol, deionized water, and NH(4) F. Silver particles with a size of 2-50 nm were deposited on the surface using the sputter deposition technique. Calcium phosphate coatings were grown on the nanotubular titania by simple immersion in Hanks' solution. It has been found that the silver nanoparticles are distributed homogeneously in the coating, which is promising for maintaining a steady antibacterial effect. The results show also that the Ag-incorporated TiO(2) nanotubes significantly stimulate apatite deposition from Hanks' solution. The highly ordered Ag-incorporated TiO(2) nanotube arrays with apatite coating may offer unique surface features for biomedical implants, ensuring both biocompatibility and antibacterial properties.

Multiscale characterization of nanostructured Al-Si-Zr alloys obtained by rapid solidification method.

Properties of engineering metallic alloys (e.g., fracture toughness, corrosion resistance) are often limited by the presence of primary intermetallic particles which form during conventional solidification. Rapid solidification brings about much more homogenous amorphous and/or nanocrystalline structure with reduced density of primary particles. Rapidly solidified thin ribbons obtained by melt spinning are usually considered as intrinsically homogenous. However, due to different cooling conditions at the wheel surface and on the side exposed to the ambient environment, structure of such ribbons may vary significantly across its thickness. The materials studied in this study were 30-40 µm thickness ribbons of nanocrystalline hyper- and hypo-eutectic Al-Si-Zr alloys produced by melt-spinning method. Transmission electron microscopy and high resolution scanning transmission electron microscopy were used to characterize the structure homogeneity across the ribbons. Thin foils for transmission observations were prepared by focused ion beam system. Microstructural observations confirmed nanocrystalline character of Al-Si-Zr alloys. However, these observations revealed inhomogeneity of the structure across the ribbon width.