The influence of hydrogen plasma pre-treatment on the structure of BDND electrode surface applied for phenol detection

The surface properties of boron-doped nanocrystalline diamond films treated with H(2) plasma was investigated in regard to their electrochemical response for phenol oxidation. The surface of these films is relatively flat formed by crystallites with sizes of about 40 nm. X-ray photoelectron spectroscopy analyses showed that electrode surface has a high amount of C-H bonds. This behavior is in agreement with Mott-Schottky plot measurements concerning the flat band potential that presented a value as expected for hydrogenated diamond surface. This electrode presented the phenol detection limit of 0.08 mg L(-1) for low phenol concentrations from 40 to 250 mu mol L(-1).

Characterization of Si : O : C : H films fabricated using electron emission enhanced chemical vapour deposition

Silicon-based polymers and oxides may be formed when vapours of oxygen-containing organosilicone compounds are exposed to energetic electrons drawn from a hot filament by a bias potential applied to a second electrode in a controlled atmosphere in a vacuum chamber. As little deposition occurs in the absence of the bias potential, electron impact fragmentation is the key mechanism in film fabrication using electron-emission enhanced chemical vapour deposition (EEECVD). The feasibility of depositing amorphous hydrogenated carbon films also containing silicon from plasmas of tetramethylsilane or hexamethyldisiloxane has already been shown. In this work, we report the deposition of diverse films from plasmas of tetraethoxysilane (TEOS)-argon mixtures and the characterization of the materials obtained. The effects of changes in the substrate holder bias (Vs) and of the proportion of TEOS in the mixture (XT) on the chemical structure of the films are examined by infrared-reflection absorption spectroscopy (IRRAS) at near-normal and oblique incidence using unpolarised and p-polarised, light, respectively. The latter is particularly useful in detecting vibrational modes not observed when using conventional near-normal incidence. Elemental analyses of the film were carried out by X-ray photoelectron spectroscopy (XPS), which was also useful in complementary structural investigations. In addition, the dependencies of the deposition rate on Vs and XT are presented. (c) 2007 Elsevier B.V. All rights reserved.

Corrosion protection of stainless steel by polysiloxane hybrid coatings prepared using the sol-gel process

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Evaluation of residual iron in carbon nanotubes purified by acid treatments

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The valuable role of renucleation rate in ultrananocrystalline diamond growth

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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.

Study of superficial properties of titanium treated by PIIID

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Diverse Amorphous Carbonaceous Thin Films Obtained by Plasma Enhanced Chemical Vapor Deposition and Plasma Immersion Ion Implantation and Deposition

Diverse amorphous hydrogenated carbon and similar films containing additional elements were produced by Plasma Enhanced Chemical Vapor Deposition (PECVD) and by Plasma Immersion Ion Implantation and Deposition (PIIID). Thus a-C:H, a-C:H:F, a-C:H:N, a-C:H:Cl and a-C:H:O:Si were obtained, starting from the same feed gases, using both techniques. The same deposition system supplied with radiofrequency (RF) power was used to produce all the films. A cylindrical stainless steel chamber equipped with circular electrodes mounted horizontally was employed. RF power was fed to the upper electrode; substrates were placed on the lower electrode. For PIIID negative high tension pulses were also applied to the lower electrode. Raman spectroscopy confirmed that all the films are amorphous. Chemical characterization of each pair of films was undertaken using Infrared Reflection Absorption Spectroscopy and X-ray Photoelectron Spectroscopy. The former revealed the presence of specific structures, such as C-H, C-O, O-H. The latter allowed calculation of the ratio of hetero-atoms to carbon atoms in the films, e. g. F:C, N:C, and Si:C. Only relatively small differences in elemental composition were detected between films produced by the two methods. The deposition rate in PIIID is generally reduced in relation to that of PECVD; for a-C:H:Cl films the reduction factor is almost four.

Preparation and characterization of glass-ceramic materials in the BaO-Li2O-ZrO2-SiO2 system and their dependence on treatment temperatures

The preparation and characterization of transparent glass-ceramics in the composition of 30Li2O:5ZrO2:xBaO:(100-x) SiO2 with x = 0, 5, 10, 15, and 20 mol% are described. Glasses were melted in a platinum crucible at 1100°C for 2 h and then heat-treated at 900°C for 3 h. The characterizations were performed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman and infrared spectroscopy, and scanning electron microscopy (SEM). The experimental results indicate that there was a structural change in the glass-ceramics as the BaO concentration in the mixture increased. In the XRD patterns of samples without heat treatment, only the halo was observed. After heat treatment, the appearance of the materials was verified by X-ray diffraction peaks. The reorganization of the amorphous solid was confirmed by Raman and IR spectroscopy along with XPS and SEM, with a more homogeneous phase formation being observed.

Polymer treatment by plasma immersion ion implantation of nitrogen for formation of diamond-like carbon film

Nitrogen ions were implanted by plasma immersion in Kapton, Mylar and polypropylene, with the objective of forming a diamond-like carbon layer on these polymers. The Raman spectrum of the implanted polypropylene showed typical Diamond-Like Carbon (DLC) graphite (G) and disorder (D) peaks, with an sp 3/sp2 hybridization ratio of approximately 0.4 to 0.6. The XPS analysis of the three implanted polymers also showed peaks of C-C and N-C bonds in the sp3 configuration, with hybridization ratios in the same range as the Raman result. The implanted polymers were exposed to oxygen plasma to test the resistance of the polymers to oxygen degradation. Mass loss rate results, however, showed that the DLC layer formed is not sufficiently robust for this application. Nevertheless, the layer formed can be suitable for other applications such as in gas barriers in beverage containers. Further study of implantation conditions may improve the quality of the DLC layer.

An ellipsometric study of manganese oxide films: In situ characterization of the deposition and electroreduction of MnO2

The electrodeposition of manganese oxide films onto a platinum substrate was investigated by means of in situ ellipsometry. In the thickness range from 0 to 150 nm, the anodic oxide behaves as an Isotropic single layer with optical constants that are independent of thickness. Deviations at higher thickness are explained in terms of anisotropic properties of the film. The electroreduction of thin films (up to ca. 150 nm) in an alkaline electrolyte leads to a decrease in both the refractive index and the extinction coefficient and is accompanied by a thickness increase of ca. 10%. The Mn(IV) to Mn(III) conversion takes place from the oxide/electrolyte interface inwards. © 2004 The Electrochemical Society. All rights reserved.

Corrosion protection of fluorzirconate glasses coated by a layer of surface modified tin oxide nanoparticles

The protection efficiency against water corrosion of fluorozirconate glass, ZBLAN, dip-coated by nanocrystalline tin oxide film containing the organic molecule Tiron® was investigated by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The chemical bonding structure of the surface region and morphology were studied before and after two water exposure periods of 5 and 30 min. The results of the analysis for the as-grown sample revealed a SnO1.6 phase containing carbon and sulfur, related to Tiron®, and traces of elements related to ZBLAN (Zr, F, Ba). This fact and the clear evidence of the presence of tin oxifluoride specie (SnOxF y) indicates a diffusion of the glass components into the porous coating. After water exposure, the increase of the oxygen concentration accompanied by a strong increase of Zr, F, Ba and Na content is interpreted as filling of the nanopores of the film by glass compounds. The formation of a compact protective layer is supported by the morphological changes observed by AFM. © 2005 Elsevier B.V. All rights reserved.

Structure and properties of Ti4+-Ureasil organic-inorganic hybrids

Hybrid planar waveguides were prepared from Ti4+-acetylacetone (acac)-Ureasil sols deposited on glass substrates. Structural features have been investigated by spectroscopic measurements (Fourier Transform Infrared Spectroscopy (FTIR), X-ray Photoelectron Spectroscopy (XPS) and Raman scattering) and Small Angle X-ray Scattering (SAXS). Addition of Ti 4+-acac to the ureasil (Ti:Si molar ratio 1:1) leads to the formation of bonds between the Ti complex and the siloxane groups, whereas further addition of Ti4+ (Ti:Si molar ratio 5:1) leads to the additional formation of titanium-rich nanoclusters. The optical parameters of the waveguides such as refractive index, thickness, propagating modes and attenuation coefficient were measured at 632.8, 543.5 and 1550 nm by the prism coupling technique. The refractive index can be tuned by the Ti4+ relative content. The few microns thick planar waveguides support well confined propagating modes with low attenuation loss for all compositions. ©2006 Sociedade Brasileira de Química.

Characterization and in vitro cytocompatibility of an acid-etched titanium surface

The aims of this study were to characterize the microstructure of a commercially pure titanium (cpTi) surface etched with HCl/H 2SO 4 (AE-cpTi) and to investigate its in vitro cytocompatibility compared to turned cpTi (T-cpTi). T-cpTi showed a grooved surface and AE-cpTi revealed a surface characterized by the presence of micropits. Surface parameters indicated that the AE-cpTi surface is more isotropic and present a greater area compared to T-cpTi. The oxide film thickness was similar between both surfaces; however, AE-cpTi presented more Ti and O and less C. Osteoblastic cell proliferation, alkaline phosphatase activity, and bone-like nodule formation were greater on T-cpTi than on AE-cpTi. These results show that acid etching treatment produced a surface with different topographical and chemical features compared to the turned one, and such surface modification affected negatively the in vitro cytocompatibility of cpTi as demonstrated by decreasing culture growth and expression of osteoblastic phenotype.

PtSnIr/C anode electrocatalysts: Promoting effect in direct ethanol fuel cells

This study investigates the promoting effect of PtSnIr/C (1:1:1) electrocatalyst anode, prepared by polymeric precursor method, on the ethanol oxidation reaction in a direct ethanol fuel cell (DEFC). All of the materials used were 20% metal m/m on carbon. X-ray photoelectron spectroscopy (XPS) analysis showed the presence of Pt, PtOH 2, PtO 2, SnO 2 and IrO 2 at the electrocatalyst surface, indicating a possible decorated particle structure. X-ray diffractometry (XRD) analysis indicated metallic Pt and Ir as well as the formation of an alloy with Sn. Using the PtSnIr/C electrocatalyst prepared here with two times lower loading of Pt than PtSn/C E-tek electrocatalyst, it was possible to obtain the same maximum power density found for the commercial material. The main reaction product was acetic acid probably due to the presence of oxides, in this point the bifunctional mechanism is predominant, but an electronic effect should not be discarded. © 2012 Sociedade Brasileira de Química.