Influence of strains and defects on ferroelectric and dielectric properties of thin-film barium-strontium titanates

Pristine, W and Mn 1% doped Ba(0.6)Sr(0.4)TiO(3) epitaxial thin films grown on the LaAlO(3) substrate were deposited by pulsed laser deposition (PLD). Dielectric and ferroelectric properties were determined by the capacitance measurements and X-ray diffraction was used to determine both residual elastic strains and defect-related inhomogeneous strains-by analyzing diffraction line shifts and line broadening, respectively. We found that both elastic and inhomogeneous strains are affected by doping. This strain correlates with the change in Curie-Weiss temperature and can qualitatively explain changes in dielectric loss. To explain the experimental findings, we model the dielectric and ferroelectric properties of interest in the framework of the Landau-Ginzburg-Devonshire thermodynamic theory. As expected, an, elastic-strain contribution due to the epilayer-substrate misfit has an important influence on the free-energy. However, additional terms that correspond to the defect-related inhomogeneous strain had to be introduced to fully explain the measurements.

Evaluation of color removal and degradation of a reactive textile azo dye on nanoporous TiO2 thin-film electrodes

The feasibility of the photobleaching of a textile azo dye, reactive orange 16 (C.I. 17757), in aqueous solution using titanium dioxide thin-film electrodes prepared by the sol-gel method was investigated. The best conditions for maximum photoelectrocatalytic degradation were found to be pH > 10 for Na2SO4 medium and pH < 6 for NaCl. In both situations, an applied potential of +1.0 V and low dye concentration are recommended, when 100% of color removal is obtained after 20 min of photoelectrocatalysis. The effects of side reaction pathway on the degradation rate of dye in sulfate and chloride medium were presented and the best performance are optimized to situations closed to that verified in the textile effluent. The influence of variables as applied potential, pH, supporting electrolyte and dye concentration on the kinetics of photoelectrochemical degradation also were investigated. Oxalic acid is identified by HPLC and UV-Vis spectrophotometric methods as the main degradation product generated after 180 min of photoelectrocatalysis of 4 x 10(-5) mol l(-1) dye in sodium sulphate pH 12 and NaCl pH 4.0 and a maximum reduction of 56 and 62% TOC was obtained, respectively. (C) 2004 Elsevier Ltd. All rights reserved.

A new amperometric biosensor for salicylate based on salicylate hydroxylase immobilized on polipyrrole film doped with hexacyanoferrate

An amperometric biosensor for salicylate detection was developed by immobilizing salicylate hydroxylase via glutaraldehyde onto a polypyrrole film doped with hexacyanoferrate, supported on a glassy carbon electrode surface. The sensor monitors the catechol produced in the enzymatic reaction on the film surface, at an applied potential of 150 mV vs. SCE. A [NADH]/[salicylate] ratio between 2 and 4 gave the best response. The biosensor presented the best performance in a solution with pH=7.4. The response time was about 40 s. A linear range of response was observed for salicylate concentrations between 1.0x10(-5) and 1.0x10(-4) mol l(-1) and the equation adjusted for this curve was I=(-0.04+/-0.01)+(11.4+/-0.2)[salicylate] with a correlation coefficient of 0.999 for n=6. The biosensor retains its activity for at least 10 days despite daily use. The results obtained using the biosensor for salicylate determination, in three different samples of antithermic drugs, presented a good correlation with the standard colorimetric method.

Electrochemical impedance spectroscopy characterization of passive film formed on implant Ti-6Al-7Nb alloy in Hank's solution

The influence of potential on electrochemical behavior of Ti-6Al-7Nb alloy under simulate physiological conditions was investigated by electrochemical impedance spectroscopy (EIS). The experimental results were compared with those obtained by potentiodynamic polarization curves. All measurements were carried out in Hank's aerated solution at 25degreesC, at pH 7.8 and at different potentials (corrosion potential, 0 mV(SCE), 1000 mV(SCE), and 2000 mV(SCE)). The EIS spectra exhibited a two-step or a two-time constant system, suggesting the formation of a two-layer oxide film on the metal surface. The high corrosion resistance, displayed by this alloy in electrochemical polarization tests, is due to the dense inner layer, while its osseointegration ability can be ascribed to the presence of the outer porous layer. (C) 2004 Kluwer Academic Publishers.

Anodic oxidation of formaldehyde on Pt-modified SnO2 thin film electrodes prepared by a sol-gel method

Pt-modified SnO2 electrodes were prepared onto titanium substrates in the form of thin films of similar to2 mum at different temperatures in the range from 200 to 400degreesC. Surface morphology was examined by scanning electron microscopy (SEM). It was found that Pt-SnO2 sol-gel layers are significantly rough and have a low porosity. X-ray diffraction (XRD) studies showed that the films consist of Pt nanoparticles with average size varying from about 5 to 10 nm, depending on the preparation temperature, and amorphous tin oxide. X-ray photoelectron spectroscopy (XPS) was employed to determine the superficial composition of the electrodes and demonstrated the presence of Sn4+ in all the samples. XPS spectra of the Pt 4f electrons showed the presence of Pt in the zero-valence state as well as in ionic forms. The general electrochemical behavior was characterized by cyclic voltammetry in 1 mol l(-1) HClO4 and the electrocatalytic activity towards the oxidation of formaldehyde was investigated by potential sweeps and chronoamperometry. The results obtained show that the Pt-SnO2/Ti system exhibits a significant catalytic activity for the oxidation of formaldehyde, with an onset potential below 0.1 V. (C) 2004 Elsevier Ltd. All rights reserved.

Effects of post-annealing on the dielectric properties of Au/BaTiO3/Pt thin film capacitors

Barium titanate thin films were prepared by the polymeric precursor method and deposited onto Pt/Ti/SiO2/Si substrates. X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FT-IR) and micro-Raman spectroscopy were used to investigate the formation of the BaTiO3 perovskite phase. Afterwards, the films were submitted to post-annealing treatments in oxygen and nitrogen atmospheres at 300 degreesC for 2 h, and had their dielectric properties measured. It was observed that the electric properties of the thin films are very sensitive to the nature of the post-annealing atmosphere. This study demonstrates that post-annealing in an oxygen atmosphere increases the dielectric relaxation phenomenon and that post-annealing in a nitrogen atmosphere produces a slight dielectric relaxation. (C) 2004 Elsevier B.V All rights reserved.

Film formation and surface growth on tin electrodes in bicarbonate solutions: an impedance spectroscopy study

The electrochemical behaviour of potentiodynamically formed thin anodic films of polycrystalline tin in aqueous sodium bicarbonate solutions (pH approximate to 8.3) were studied using cyclic voltammetry and electrochemical impedance spectroscopy. Different equivalent circuits corresponding to various potential regions were employed to account for the electrochemical processes taking place under each condition. (C) 2004 Elsevier Ltd. All rights reserved.

The characterisation of the protective film formed by benzotriazole on the 90/10 copper-nickel alloy surface in H2SO4 media

The nature of the protective film formed by benzotriazole (BTAH) on the surface of the 90/10 CuNi alloy in deaerated 0.5 mol L-1 H2SO4 solution containing Fe(III) ions as oxidant was investigated by weight-loss, calorimetric measurements, and by surface-enhanced Raman spectroscopy (SERS). The SERS measurements show that the protective film is composed by the [Cu(I)BTA](n), polymeric complex and that the BTAH molecules are also adsorbed on the electrode surface. A modification of the BET isotherm for adsorption of gases ill solids is proposed to describe the experimental results obtained from weight-loss experiments that suggest an adsorption in multilayers. Electrochemical studies of copper and nickel in 0.5 mol L-1 H2SO4 in presence and absence of BTAH have also been made as an aid to interpret the results. The calculated adsorption free energy of the cuprous benzotriazolate on the surface of the alloy is in accordance with the value for pure copper. (C) 2007 Elsevier Ltd. All rights reserved.

Effect of the fluorination of DLC film on the corrosion protection of aluminum alloy (AA 5052)

It is presented a study conducted on the physical and electrochemical properties of fluorinated a-C:H films deposited onto a commercial aluminum alloy (AA 5052). The coatings were deposited from mixtures of 91% of acetylene and 9% of argon by plasma immersion ion implantation and deposition technique, PIIID. Total gas pressure was 44 Pa and deposition time (t(dep)) was varied from 300 to 1200 s. The depositing plasmas were generated by the application of radiofrequency power (13.56 MHz, 100W) to the upper electrode and high voltage negative pulses (2400 V. 300 Hz) to the sample holder. Fluorine was incorporated in a post-deposition plasma treatment (13.56 MHz, 70W, 13 Pa) generated from sulfur hexafluoride atmosphere. Chemical structure and composition of the films were investigated using infrared reflectance/absorbance spectroscopy and X-ray photoelectron spectroscopy. The corrosion resistance of the layers was determined by electrochemical impedance spectroscopy (EIS) in a 3.5% NaCl solution, at room temperature. Films presented good adhesion to the substrates and are classified as hydrogenated amorphous carbon (a-C:H) with oxygen traces. Fluorine was detected in all the samples after the post-deposition treatment being its proportion independent on the deposition time. Film thickness presented different tendencies with t(dep), revealing the variation of the deposition rate as a function of the deposition time. Such fluorinated a-C:H films improved the corrosion resistance of the aluminum surface. In a general way the corrosion resistance was higher for films prepared with lower deposition times. The variation of sample temperature with t(dep) was found to be decisive for the concentration of defects in the films and, consequently, for the performance of the samples in electrochemical tests. Results are interpreted in terms of the energy delivered to the growing layer by ionic bombardment. (C) 2010 Elsevier B.V. All rights reserved.

One-dimensional analytical model for oxide thin film growth on Ti metal layers during laser heating in air

This paper presents the theoretical and experimental results for oxide thin film growth on titanium films previously deposited over glass substrate. Ti films of thickness 0.1 μm were heated by Nd:YAG laser pulses in air. The oxide tracks were created by moving the samples with a constant speed of 2 mm/s, under the laser action. The micro-topographic analysis of the tracks was performed by a microprofiler. The results taken along a straight line perpendicular to the track axis revealed a Gaussian profile that closely matches the laser's spatial mode profile, indicating the effectiveness of the surface temperature gradient on the film's growth process. The sample's micro-Raman spectra showed two strong bands at 447 and 612 cm -1 associated with the TiO 2 structure. This is a strong indication that thermo-oxidation reactions took place at the Ti film surface that reached an estimated temperature of 1160 K just due to the action of the first pulse. The results obtained from the numerical integration of the analytical equation which describes the oxidation rate (Wagner equation) are in agreement with the experimental data for film thickness in the high laser intensity region. This shows the partial accuracy of the one-dimensional model adopted for describing the film growth rate. © 2001 Elsevier Science B.V.

Photoelectrocatalytic degradation of Remazol Brilliant Orange 3R on titanium dioxide thin-film electrodes

Degradation of reactive dye Remazol Brilliant Orange 3R (RBO) has been performed using photoeletrocatalysis. A biased potential is applied across a titanium dioxide thin-film photoelectrode illuminated by UV light. It is suggested that charges photogenerated at the electrode surface give rise to chlorine generation and powerful oxidants (OH) that causes the dye solution to decolorize. Rate constants calculated from color decay versus time reveal a first-order reaction up to 5.0×10-5 mol l-1 in dye concentration. The best experimental conditions were found to be pH 6.0 and 1.0 mol l-1 NaCl when the photoelectrode was biased at +1V (versus SCE). Almost complete mineralization of the dye content (70% TOC reduction) was achieved in a 3-h period using these conditions. Effects of other electrolytes, dye concentration and applied potentials also have been investigated and are discussed. © 2003 Elsevier Science B.V. All rights reserved.

Photoelectrocatalytic production of active chlorine on nanocrystalline titanium dioxide thin-film electrodes

The production of chlorine and hypochlorite is of great economical and technological interest due to their large-scale use in many kinds of commercial applications. Yet, the current processes are not without problems such as inevitable side reactions and the high cost of production. This work reports the photoelectrocatalytic oxidation of chloride ions to free chlorine as it has been investigated by using titanium dioxide (TiO2) and several metal-doped titanium dioxide (M-TiO2) material electrodes. An average concentration of 800 mg L-1 of free chlorine was obtained in an open-air reactor using a TiO2 thin-film electrode biased at +1.0 V (SCE) and illuminated by UV light. The M-doped electrodes have performed poorly compared with the pure TiO2 counterpart. Test solutions containing 0.05 mol L-1 NaCl pH 2.0-4.0 were found to be the best conditions for fast production of free chlorine. A complete investigation of all parameters that influence the global process of chlorine production by the photoelectrocatalytic method such as applied potential, concentration of NaCl, pH solution, and time is presented in detail. In addition, photocurrent vs potential curves and the reaction order are also discussed.

Effect of resin luting film thickness on fracture resistance of a ceramic cemented to dentin

Purpose: The aim of this study was to evaluate the fracture resistance of ceramic plates cemented to dentin as a function of the resin cement film thickness. Materials and Methods: Ceramic plates (1 and 2 mm thicknesses) were cemented to bovine dentin using resin composite cement. The film thicknesses used were approximately 100, 200, and 300 μm. Noncemented ceramic plates were used as control. Fracture loads (N) were obtained by compressing a steel indenter in the center of the ceramic plates. ANOVA and Tukey tests (α = 0.05) were used for each ceramic thickness to compare fracture loads among resin cement films used. Results: Mean fracture load (N) for 1-mm ceramic plates were: control - 26 (7); 100 μm - 743 (150); 200 μm - 865 (105); 300 μm - 982 (226). Test groups were significantly different from the control group; there was a statistical difference in fracture load between groups with 100 and 300 μm film thicknesses (p < 0.01). Mean fracture load for 2-mm ceramic plates were: control - 214 (111); 100 μm - 1096 (341); 200 μm - 1067 (226); 300 μm - 1351 (269). Tested groups were also significantly different from the control group (p < 0.01). No statistical difference was shown among different film thicknesses. Conclusions: Unluted specimens presented significantly lower fracture resistance than luted specimens. Higher cement film thickness resulted in increased fracture resistance for the 1-mm ceramic plates. Film thickness did not influence the fracture resistance of 2-mm porcelain plates. Copyright © 2007 by The American College of Prosthodontists.