Effect of Na2SiO3 on synthesis of TiO2 nanopowders by thermal processing of the precursor

TiO₂ nanopowders could be prepared by thermal processing of the precursor of titanium hydroxide, urea and Na₂SiO₃. The powders were characterized by X-ray diffractometry, scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. The results show that Na₂SiO₃ has an important effect on the average crystallite size and dispersity of TiO₂ nanopowders, and other phases (Na₂SO₄ and SiO₂) will be introduced. However, Na₂SO₄ has distinctive intercalation ability and catalytic activity; SiO₂ coating layers can effectively inhibit the agglomeration of TiO₂ nanopowders. TiO₂ (anatase) powders with well dispersity can be prepared at ～600 °C for 2 h with addition of 2–6 wt.% Na₂SiO₃, and the average crystallite size is 15.5–22.1 nm. The surface of the sample mainly consists of Ti, O, C, Si, Na and S six species elements.     

CdS nanoparticles incorporated onion-like mesoporous silica films: Ageing-induced large stokes shifted intense PL emission

CdS nanoparticles (NPs) were generated in onion-like ordered mesoporous SiO₂ films through a modified sol–gel process using P123 as a structure directing agent. Initially Cd²⁺ doped (12 equivalent mol% with respect to the SiO₂) mesoporous SiO₂ films were prepared on glass substrate. These films after heat-treatment at 350 °C in air yielded transparent mesoporous SiO₂ films having hexagonally ordered onion-like pore channels embedded with uniformly dispersed CdO NPs. The generated CdO NPs were transformed into CdS NPs after exposing the films in H₂S gas at 200 °C for 2 h. The as-prepared CdS NPs incorporated mesoporous SiO₂ films (transparent and bright yellow in color) showed a band-edge emission at 485 nm and a weak surface defect related emission at 530 nm. During ageing of the films in ambient condition the band-edge emission gradually weakened with time and almost disappeared after about 15 days with concomitant increase of defect related strong surface state emission band near 615 nm. This transformation was related to the decay of initially formed well crystalline CdS to relatively smaller and weakly crystalline CdS NPs with surface defects due to gradual oxidation of surface sulfide. At this condition the embedded CdS NPs show large Stokes shifted (∼180 nm) intense broad emission which could be useful for luminescent solar concentrators. The detailed process was monitored by UV–Visible, FTIR and Raman spectroscopy, XPS, XRD and TEM studies. The evolution of photoluminescence (PL) and life times of CdS/SiO₂ films were monitored with respect to the ageing time.     

Photocatalytic degradation of gaseous toluene over TiO2–SiO2 composite nanotubes synthesized by sol–gel with template technique

TiO₂–SiO₂ composite nanotubes were successfully synthesized by a facile sol–gel technique utilizing ZnO nanowires as template. The nanotubes were well characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, N₂ adsorption–desorption analysis and UV–vis diffuse reflectance spectroscopy. The nanotubular TiO₂–SiO₂ composite photocatalysts showed diameter of 300–325 nm, fine mesoporous structure and high specific surface area. The results indicated that the degradation efficiency of gaseous toluene could get 65% after 4 h reaction using the TiO₂–SiO₂ composite as the photocatalyst under UV light illumination, which was higher than that of P25.     

Formation of silicon dioxide layers at low temperatures (150-400 °C) by atmospheric pressure plasma oxidation of silicon

The formation of silicon dioxide (SiO₂) layers at low temperatures (150-400 °C) by atmospheric pressure plasma oxidation of Si(0 0 1) wafers have been studied using a gas mixture containing He and O₂. A 150 MHz very high frequency (VHF) power supply was used to generate high-density atomic oxygen in the atmospheric pressure plasma. Oxidation rate, structure, and thickness and refractive index profiles of the oxidized layers were investigated by ellipsometry and infrared absorption spectroscopy. Atomic force microscopy was also employed to observe atomic-scale morphologies of the layer surface and wafer Si surface, after chemical removal of the oxidized layers. It was found that stoichiometric SiO₂ layers were obtained at higher oxidation rates than conventional dry O₂ thermal oxidation and radical oxidation processes, even at a very low substrate temperature of 150 °C. Although thickness variations were observed in the plasma region, the refractive index was independent of both substrate temperature and VHF power. In addition, the SiO₂ surface and SiO₂/Si interface roughnesses were comparable to those obtained in conventional dry oxidation at high temperatures.     

Origin of photoluminescence peaks in Ge–SiO2 thin films

Ge–SiO₂ thin films were prepared by the RF magnetron sputtering technique on p-Si substrates from a Ge–SiO₂ composite target. The as-deposited films were annealed in the temperature range of 300–1000 °C under nitrogen ambience. The structure of films was evaluated by X-ray diffraction, X-ray photoemission spectroscopy and Fourier transform infrared absorption spectroscopy. Results show that the content of Ge and its oxides in the films change with increasing annealing temperature (T_a), the photoluminescence (PL) characteristics are closely dependent on the contents of Ge and its oxides in SiO₂ matrix. The dependence observed strongly suggests that the PL peak at 394 nm is related to the existence of GeO and 580 nm to that of Ge nanocrystal (nc-Ge) in the films.     

Heteroepitaxial growth of δ-Bi2O3 thin films on CaF2(1 1 1) by chemical vapour deposition under atmospheric pressure

We have succeeded in achieving the heteroepitaxial growth of a δ-Bi₂O₃ thin film on a CaF₂(1 1 1) substrate by means of chemical vapour deposition under atmospheric pressure. The film grew with a strong (1 1 1) orientation. From X-ray pole figures, it was observed that the δ-Bi₂O₃ film grew on the CaF₂(1 1 1) substrate with 60° rotational in-plane domains. The growth mode was of a 3D island type, and the grain size decreased with increasing oxygen pressure during the δ-Bi₂O₃ film growth, improving the overall surface smoothness.     

The corrosion resistance of Nitinol alloy in simulated physiological solutions Part 2: The effect of surface treatment

The effect of surface treatment – boiling in water and thermal oxidation at temperatures up to 600 °C – on the corrosion behavior of Nitinol was investigated in simulated Hanks physiological solution using electrochemical polarization methods. Morphological and compositional properties of the modified surfaces were analyzed by scanning electron microscopy, X-ray photoelectron spectroscopy and Auger electron spectroscopy depth profiling. Surface preparation – grinding or polishing – is shown to have a decisive role in the degree of improvement of corrosion properties by surface treatments. Low temperature treatments like boiling in water and thermal oxidation at 100 °C resulted in the formation of oxide layers only a few nanometers thick, and composed mainly of TiO₂ and a small amount of NiO. These layers are well able to protect the underlying Nitinol substrate. Up to 500 °C, surface preparation directly determines the thickness of the oxide scale, as a 20-fold difference in thickness is observed between ground and polished samples. At higher temperatures, the oxide thickness was similar for the two samples. A multilayer structure is observed at all temperatures investigated. The outermost layer at the oxide/air interface is composed of TiO₂ and NiO, while the interior of the oxide scale is composed exclusively of TiO₂. Oxide layers formed by thermal oxidation at elevated temperatures also improve the corrosion characteristics of Nitinol, especially for polished substrates.     

Enhanced apatite formation on Ti metal heated in PO2-controlled nitrogen atmosphere

The oxynitridation of biomedical titanium metal under a precisely regulated oxygen partial pressure (P_O2) of 10^? 14 Pa in nitrogen atmosphere at 973 K for 1 h strongly enhanced apatite formation compared with that on Ti heated in air. The factors governing the high apatite-forming ability are discussed from the viewpoint of the surface properties of Ti heated under a P_O2 of 10^? 14 Pa in nitrogen atmosphere determined from X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and zeta potential measurements. Nitrogen (N)-doped TiO₂ (interstitial N) was formed on pure Ti heated under a P_O2 of 10^? 14 Pa in nitrogen atmosphere at 973 K. The XPS O1s main peak shifted toward a lower binding energy upon heating under a P_O2 of 10^? 14 Pa. This shift may be due to the formation of oxygen vacancies. This Ti surface had a positive zeta potential of approximately 20 mV. According to time-of-flight secondary ion mass spectroscopy results, PO₄^3 ? ions were predominantly adsorbed on Ti soaked in simulated body fluid (SBF) after heat treatment, followed by calcium ions. It was concluded that the apatite formation kinetics can be described using the Avrami–Erofeev equation with an Avrami index of n = 2, which implies the instantaneous nucleation of apatite on the surface of Ti soaked in SBF after heat treatment at 973 K under a P_O2 of 10^? 14 Pa.     

Titanium–SiO2 nanocomposites and their scaffolds for dental applications

There have been a number of attempts to modify the properties of titanium implants to improve osseointegration. These modifications include alterations of the chemistry and roughness of the surface of the implant. In this work, Ti–10 wt.% SiO₂ nanocomposites and their scaffolds were synthesized using a combination of mechanical alloying and a “space-holder” sintering process. The phase and microstructure analysis was carried out using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and the properties were measured using hardness and corrosion testing equipment. An amorphous structure was obtained at 20 h of milling. The crystallization of the amorphous phase upon annealing led to the formation of a nanostructured Ti–10 wt.% SiO₂ composite with a grain size of approximately 40 nm. The Vickers hardness of the Ti–10 wt.% SiO₂ nanocomposites reached 670 HV_0.2. The in vitro cytocompatibility of these materials was evaluated and compared with conventional microcrystalline titanium, where normal human osteoblast (NHOst) cells from Cambrex (CC-2538) were cultured. The morphology of the cell cultures obtained on the bulk Ti–10 wt.% SiO₂ nanocomposite was similar to those obtained on the microcrystalline titanium. However, on the porous scaffold, the cells adhered to the insert that penetrated the porous structure with their entire surface, whereas on the polished surface, more spherical cells were observed with a smaller surface of adhesion. Porous Ti–10 wt.% SiO₂ scaffolds have been developed in order to promote bone ingrowth and to induce prosthesis stabilization.     

Hydrothermal synthesis of single-crystal VO2(B) nanobelts

Single crystalline VO₂(B) nanobelts with a metastable structure were obtained through a simple hydrothermal synthetic method. The VO₂(B) nanobelts were characterized by means of X-ray diffraction, transmission electron microscopy, selected area electronic diffraction, field-emission scanning electron microscopy and X-ray energy-dispersive spectroscopy techniques. The as-obtained VO₂(B) nanobelts are 400–600 nm long, typically 100–150 nm wide and 20–30 nm thick. The belt-like VO₂(B) with a high surface area may be beneficial to lithium insertion between the VO₆ layers for application in batteries.     

Synthesis and luminescence properties of highly uniform SiO2@LaPO4:Eu3+ core–shell phosphors

SiO₂@LaPO₄:Eu³⁺ core–shell phosphors have been successfully synthesized by a one-step and economical wet-chemical route at low temperature. The as-obtained products were characterized by means of photoluminescence spectroscopy (PL), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive spectrometer (EDS) and X-ray photoelectron spectroscopy (XPS). The SEM, EDS and XPS analysis indicate that SiO₂@LaPO₄:Eu³⁺ core–shell phosphors can only be synthesized in a pH range of 8–11 and the possible mechanism has been proposed. The XRD results demonstrate that the structure of LaPO₄:Eu³⁺ layers is transferred into monoclinic phase from hexagonal phase after annealing at 800 °C for 2 h. The SiO₂@LaPO₄:Eu³⁺ phosphors show strong orange–red luminescence under ultraviolet excitation. The relative emission intensity of Eu³⁺ increases with increasing the annealing temperature and the number of coating cycles, and the optimum concentration for Eu³⁺ was determined to be 5 mol% of La³⁺ in SiO₂@LaPO₄ phosphors.     

Tannin-immobilized mesoporous silica bead (BT–SiO2) as an effective adsorbent of Cr(III) in aqueous solutions

This study describes a new approach for the preparation of tannin-immobilized adsorbent by using mesoporous silica bead as the supporting matrix. Bayberry tannin-immobilized mesoporous silica bead (BT–SiO₂) was characterized by powder X-ray diffraction to verify the crystallinity, field-emission scanning electron microscopy to observe the surface morphology, and surface area and porosity analyzer to measure the mesoporous porous structure. Subsequently, the adsorption experiments to Cr(III) were applied to evaluate the adsorption performances of BT–SiO₂. It was found that the adsorption of Cr(III) onto BT–SiO₂ was pH-dependent, and the maximum adsorption capacity was obtained in the pH range of 5.0–5.5. The adsorption capacity was 1.30 mmol g^?1 at 303 K and pH 5.5 when the initial concentration of Cr(III) was 2.0 mmol L^?1. Based on proton nuclear magnetic resonance (HNMR) analyses, the adsorption mechanism of Cr(III) on BT–SiO₂ was proved to be a chelating interaction. The adsorption kinetic data can be well described using pseudo-first-order model and the equilibrium data can be well fitted by the Langmuir isothermal model. Importantly, no bayberry tannin was leached out during the adsorption process and BT–SiO₂ can simultaneously remove coexisting metal ions from aqueous solutions. In conclusion, this study provides a new strategy for the preparation of tannin-immobilized adsorbents that are highly effective in removal of heavy metals from aqueous solutions.     

Isothermal oxidation behavior of the TZAV-20 alloy

Oxidation behavior is important for secure and long-life service of metals and alloys. The isothermal oxidation behavior of the Ti–20Zr–6.5Al–4V alloy at 470 to 670 °C was investigated. The kinetics analysis shows that the oxidation of TZAV-20 alloy below 570 °C accords with the parabolic law. While the alloy oxidized at 670 °C, obeys the linear law. As oxidation temperature increases from 470 to 670 °C, the oxidation products change as: TiO₂ → TiO₂ + ZrO₂ → TiO₂ + ZrO₂ + Al₂O₃. Relation between weight gain and thickness of oxidation film shows that the weight will increase 0.171 mg/cm² for every 1 μm increasing in thickness. The surface hardness increases from approximately 380 HV for base material to 689 HV for 670 °C oxidized specimen. In short, the TZAV-20 alloy has favorable inoxidizability below 570 °C. The findings will not only promote practical applications of the new TiZrAlV series alloys but also supplement the oxidation theory.     

The photoluminescence and optical constant of ZnSe/SiO2 thin films prepared by sol–gel process

In this paper, ZnSe/SiO₂ thin films were prepared by sol–gel process. X-ray diffraction results indicate that the phase structure of ZnSe particles embedded in SiO₂ thin films is sphalerite (cubic ZnS). The dependence of ellipsometric angle ψ on wavelength λ of ZnSe/SiO₂ thin films was investigated by spectroscopic ellipsometers. The optical constant, thickness, porosity and the concentration of ZnSe/SiO₂ composite thin films were fitted according to Maxwell–Garnett effective medium theory. The thickness of ZnSe/SiO₂ thin films was also measured by surface profile. The photoluminescence properties of ZnSe/SiO₂ thin films were investigated by fluorescence spectrometer. The photoluminescence results reveal that the emission peak at 487 nm (2.5 eV) excited by 395 nm corresponds to the band-to-band emission of sphalerite ZnSe crystal (2.58 eV). Strong free exciton emission and other emission peaks corresponding to ZnSe lattice defects are also observed.     

Osteoblast interaction with laser cladded HA and SiO2-HA coatings on Ti–6Al–4V

In order to improve the bioactivity and biocompatibility of titanium endosseous implants, the morphology and composition of the surfaces were modified. Polished Ti–6Al–4V substrates were coated by a laser cladding process with different precursors: 100 wt.% HA and 25 wt.% SiO₂-HA. X-ray diffraction of the laser processed samples showed the presence of CaTiO₃, Ca₃(PO₄)₂, and Ca₂SiO₄ phases within the coatings. From in vitro studies, it was observed that compared to the unmodified substrate all laser cladded samples presented improved cellular interactions and bioactivity. The samples processed with 25 wt.% SiO₂-HA precursor showed a significantly higher HA precipitation after immersion in simulated body fluid than 100 wt.% HA precursor and titanium substrates. The in vitro biocompatibility of the laser cladded coatings and titanium substrate was investigated by culturing of mouse MC3T3-E1 pre-osteoblast cell line and analyzing the cell viability, cell proliferation, and cell morphology. A significantly higher cell attachment and proliferation rate were observed for both laser cladded 100 wt.% HA and 25 wt.% SiO₂-HA samples. Compared to 100 wt.% HA sample, 25 wt.% SiO₂-HA samples presented a slightly improved cellular interaction due to the addition of SiO₂. The staining of the actin filaments showed that the laser cladded samples induced a normal cytoskeleton and well-developed focal adhesion contacts. Scanning electron microscopic image of the cell cultured samples revealed better cell attachment and spreading for 25 wt.% SiO₂-HA and 100 wt.% HA coatings than titanium substrate. These results suggest that the laser cladding process improves the bioactivity and biocompatibility of titanium. The observed biological improvements are mainly due to the coating induced changes in surface chemistry and surface morphology.     

Potentiometric urea biosensor based on multi-walled carbon nanotubes (MWCNTs)/silica composite material

A novel potentiometric urea biosensor has been fabricated with urease (Urs) immobilized multi-walled carbon nanotubes (MWCNTs) embedded in silica matrix deposited on the surface of indium tin oxide (ITO) coated glass plate. The enzyme Urs was covalently linked with the exposed free –COOH groups of functionalized MWCNTs (F-MWCNTs), which are subsequently incorporated within the silica matrix by sol–gel method. The Urs/MWCNTs/SiO₂/ITO composite modified electrode was characterized by Fourier transform infrared (FTIR) spectroscopy, thermal gravimetric analysis (TGA) and UV–visible spectroscopy. The morphologies and electrochemical performance of the modified Urs/MWCNTs/SiO₂/ITO electrode have been investigated by scanning electron microscopy (SEM) and potentiometric method, respectively. The synergistic effect of silica matrix, F-MWCNTs and biocompatibility of Urs/MWCNTs/SiO₂ made the biosensor to have the excellent electro catalytic activity and high stability. The resulting biosensor exhibits a good response performance to urea detection with a wide linear range from 2.18 × 10^? 5 to 1.07 × 10^? 3 M urea. The biosensor shows a short response time of 10–25 s and a high sensitivity of 23 mV/decade/cm².     

Thermal oxidation of Ti6Al4V alloy: Microstructural and electrochemical characterization

Thermal oxidation (TO) of Ti6Al4V alloy was performed at 500, 650 and 800 °C for 8, 16, 24 and 48 h in air. The morphological features, structural characteristics, microhardness and corrosion resistance in Ringer's solution of TO Ti6Al4V alloy were evaluated and compared with those of the untreated one. The surface morphological features reveal that the oxide film formed on Ti6Al4V alloy is adherent to the substrate at 500 and 650 °C irrespective of the oxidation time whereas it spalls off when the alloy is oxidized at 800 °C for more than 8 h. X-ray diffraction (XRD) measurement reveals the presence of Ti(O) and α-Ti phases on alloy oxidized at 500 and 650 °C, with Ti(O) as the dominant phase at 650 °C whereas the alloy oxidized at 800 °C exhibits only the rutile phase. Almost a threefold increase in hardness is observed for the alloy oxidized at 650 °C for 48 h when compared to that of the untreated one. Thermally oxidized Ti6Al4V alloy offers excellent corrosion resistance in Ringer's solution when compared to that of the untreated alloy.     

Brazing of SiO2f/SiO2 composite modified with few-layer graphene and Invar using AgCuTi alloy

Due to the poor wettability of the AgCuTi alloy on the SiO_2f/SiO₂ composite, direct brazing of the composite with an Invar alloy could hardly achieve a reliable joint. To overcome that, the SiO_2f/SiO₂ composite was decorated with few-layer graphene (FLG) by a plasma enhanced chemical vapor deposition (PECVD) method. Sessile drop experiments indicate that the contact angle dropped from 123.8° to 50.7° after FLG was grown on the surface of the SiO_2f/SiO₂ composite. Afterwards, the effects of brazing temperature and Ti contents on the microstructure evolution and mechanical properties of joints (Invar/SiO_2f–SiO₂ modified with FLG) were investigated. The typical interface structure of the joint is SiO_2f–SiO₂/Ti₅Si₃ + TiO₂ + Cu_xTi_6 − xO(x = 2,3)/Ag(s,s) + Cu(s,s) + Cu–Ti blocks/wave-like Fe₂Ti + Ni₃Ti/Ag(s,s) + Cu(s,s) + Fe₂Ti + Ni₃Ti blocks/Invar. As the brazing temperature and Ti contents increase, the reaction layer on the SiO_2f/SiO₂ side becomes thicker and cracks gradually propagate. Meanwhile, a few dispersive Fe₂Ti + Ni₃Ti phases change into large-area wave-like compounds and more Cu–Ti compounds form with the increase of the Ti content. The microstructure evolution significantly affects the shear strength of the brazed joints. The highest shear strength is 26 MPa brazed at 860 °C for 10 min with 4.5 wt.% Ti content.     

Utilization of Si atomic steps for Cu nanowire fabrication

Techniques for controlling atomic step position at low-temperature and selective growth of Cu nanowires along the atomic step edges have been studied. By immersing the Si(111) substrates with well-defined step/terrace surfaces in the Cu-contained water with the dissolved oxygen content of less than 1 ppb, selective growth of Cu nanowires along the step edges was successfully achieved. Total reflection X-ray fluorescence spectroscopy (TXRF) revealed that the fabricated nanowires were composed of mono-atomic Cu rows. For step position control, the characteristics of step-flow pinning effect of SiO₂ films were investigated. Fine SiO₂ line patterns drawn by anodic oxidation using AFM probes enable us to obtain the step-free Si areas predetermined by the patterns.     

RBS,XRR and optical reflectivity measurements of Ti–TiO2 thin films deposited by magnetron sputtering

Single-, bi- and tri-layered films of Ti–TiO₂ system were deposited by d.c. pulsed magnetron sputtering from metallic Ti target in an inert Ar or reactive Ar + O₂ atmosphere. The nominal thickness of each layer was 50 nm. The chemical composition and its depth profile were determined by Rutherford backscattering spectroscopy (RBS). Crystallographic structure was analysed by means of X-ray diffraction (XRD) at glancing incidence. X-ray reflectometry (XRR) was used as a complementary method for the film thickness and density evaluation. Modelling of the optical reflectivity spectra of Ti–TiO₂ thin films deposited onto Si(1 1 1) substrates provided an independent estimate of the layer thickness. The combined analysis of RBS, XRR and reflectivity spectra indicated the real thickness of each layer less than 50 nm with TiO₂ film density slightly lower than the corresponding bulk value. Scanning Electron Microscopy (SEM) cross-sectional images revealed the columnar growth of TiO₂ layers. Thickness estimated directly from SEM studies was found to be in a good agreement with the results of RBS, XRR and reflectivity spectra.