Corrosion of the component phases presents in high copper dental amalgams. Application of electrochemical impedance spectroscopy and electrochemical noise analysis

The corrosion resistance of three of the constituent phases in high copper dental amalgams has been investigated by electrochemical methods in 0.9% NaCl solution. Polarization curves show corrosion potentials most positive for gamma(1)-Ag2Hg3, followed by Ag-Cu, and gamma-Ag3Sn in agreement with the order of corrosion resistance deduced from the corrosion currents. Complex plane impedance plots at the open circuit potential showed distorted semicircles with diffusional components at low frequency for Ag-Hg and Ag-Cu, while for gamma-Ag3Sn a layer of corrosion products is formed, partially or completely covering the surface of the electrode. Impedance and noise spectra have been compared in the frequency domain, and show good agreement. (C) 2004 Elsevier Ltd. All rights reserved.

Effects of thickness coating on the electrochemical behaviour of thermal spray Cr3C2-NiCr coatings

Thermally sprayed HVOF coatings are increasingly being used in industrial applications where high wear and corrosion resistance are needed [1,2]. In this paper, electrochemical ac and de experiments were used in order to obtain the corrosion resistance of coated steel with different numbers of Cr3C2-NiCr layers. This work has been performed in order to determine the role of coating thickness in the corrosion behaviour of a steel protected with cermet thermally sprayed coatings. It is known that a thicker layer protects better against corrosion when a metallic coating is evaluated. But cermet coatings, such as Cr3C2-NiCr, contain higher levels of porosity and residual stresses than metallic coatings, which really could influence the corrosion resistance of the deposited layer. Electrochemical measurements, such as Open-Circuit Potential (E-Osubset of), Polarisation Resistance (RP) and Cyclic Voltammetry (CV), were performed in an aerated 3.4 NaCI media (%wt.). Electrochemical Impedance Measurements (EIS) were also done in order to obtain a mechanism that explains the corrosion process. Structural Characterisation was carried out by means of Optical and Scanning Electron Microscopes (OM, SEM) with an Energy Dispersive Spectrometry analyser (EDS). Results show that the corrosion resistance of the complete system is mainly influenced by the substrate behaviour. The application of a higher number of deposited layers did not substantially increase their anticorrosive properties. Stress generation during the spraying deposition process plays an important role in the behaviour of the coated steel against corrosion phenomena. (C) 2002 Elsevier B.V. B.V All rights reserved.

X-ray diffraction and mossbauer spectra of nickel ferrite prepared by combustion reaction

Nickel ferrite powders with a nominal NiFe2O4 composition were synthesized by combustion reaction using urea as fuel. The powder was obtained using a vitreous silica basin heated directly on a hot plate at 480 degrees C until self-ignition occurred. After combustion, the powder was calcined at 700 degrees C for 2 h. The formation of the spinel phase and the distribution of cations in the tetrahedral and octahedral sites of the crystal structure were investigated by the Rietveld method, using synchrotron X-ray diffraction data and Mossbauer spectroscopy. The material presented a crystallite size of 120 nm and magnetic properties. The resulting stoichiometry after the Rietveld refinement was (Fe-0.989(2) Ni-0.011(2)) [Fe-1.012(2) Ni-0.989(2)] O-4.

Electrochemical behaviour of heat-treated Al-Zn-Mg alloys in chloride solutions containing sulphate

The electrochemical corrosion and passivation of Al-5Zn-1.7Mg-0.23Cu-0.053Nb alloys, submitted to different heat treatments (cold-rolled, annealed, quenched and aged, and quenched in two steps and aged), in sulphate-containing chloride solutions, has been studied by means of cyclic polarization, electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS). The cyclic polarization curves showed that sulphate addition to the chloride solution produced a poor reproducible shift of the breakdown potential to more positive potentials. The repassivation potentials, much more reproducible, and practically separating the passive from the pitting potential region, were slightly displaced in the negative direction with that addition. When the alloys were potentiodynamically polarized in the passive potential region, sulphate was incorporated in the oxide film, thus precluding chloride ingress. In addition, Zn depletion was favoured, whereas Mg losses were avoided. Different equivalent circuits corresponding to different alloys and potentials in the passive and pitting regions were employed to account for the electrochemical processes taking place in each condition. This work shows that sulphate makes these alloys more sensitive to corrosion, increasing the fracture properties of the surface layer and favouring the pitting attack over greater areas than chloride alone. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Effect of hydrogen charging on the stability of SAE 10B22 steel surface in alkaline solutions

The influence of hydrogen charging into a quenched and tempered boron steel membrane electrode (SAE 10B22) was studied using borate buffer (pH 8.4) and NaOH solutions (pH 12.7), with or without the addition of 0.01 M EDTA. At the hydrogen input side, hydrogen charging influenced cyclic voltammograms increasing the anodic charge of iron(II) hydroxide formation, and decreasing the donor density of passive films. These results suggest that the hydrogen ingress caused instability of metallic surface, increasing the surface area activity. (C) 2005 Elsevier Ltd. All rights reserved.

Comparative study of Cr3C2-NiCr coatings obtained by HVOF and hard chromium coatings

In the present work the corrosion resistance of micro-cracked hard chromium and Cr3C2-NiCr (HVOF) coatings applied on a steel substrate have been compared using open-circuit potential (E-OC) measurements, electrochemical impedance spectroscopy (EIS) and polarization curves. The coatings surfaces and cross-section were characterized before and after corrosion tests using optical microscopy (OM) and scanning electron microscopy (SEM). After 18 h of immersion, the open-circuit potential values were around -0.50 and -0.25V/(Ag vertical bar AgCl vertical bar KClsat) for hard chromium and Cr3C2- NiCr, respectively. The surface analysis done after 12 h of immersion showed iron on the hard chromium surface inside/near surface cracks, while iron was not detected on the Cr3C2-NiCr surface even after 18 h. For longer immersion time hard chromium was more degraded than thermal sprayed coating. For hard chromium coating a total resistance values between 50 and 80 k Omega cm(2) were measured and two well-defined time constants were observed, without significant change with the immersion time. For Cr3C2-NiCr coating the total impedance diminished from around 750 to 25 k Omega cm(2) as the immersion time increased from 17 up to 132 h and two overlapped time constants were also observed. Polarization curves recorded after 18 h of immersion showed a lower current and higher corrosion potential for Cr3C2-NiCr coating than other samples studied. (c) 2005 Elsevier Ltd. All rights reserved.

Electrochemical and structural characterization of heat-treated Cr3C2-NiCr coatings

The influence of heat-treatments on the electrochemical behavior of thermal spray Cr3C2-NiCr coatings prepared by high velocity oxygen fuel (HVOF) was studied in NaCl solution, at 25 degrees C, using open-circuit potential (E-OC) and electrochemical impedance spectroscopy (EIS) measurements. Coating characterization were performed before and after the heat-treatments and electrochemical tests by scanning electron microscopy, X-ray diffraction, and Auger electron spectroscopy. In addition to the changes in the original powder composition occurring during HVOF process, heat-treatment performed at 450 degrees C caused no significant changes in electrochemical response compared with untreated sample, and at 760 degrees C the main difference was the formation of a thin and defective layer of Cr2O3 at the coating surface, which increased the total impedance at the first day of immersion. Higher influence on the electrochemical was noted for samples treated at 880 degrees C, which also showed higher E-OC and total impedance, and lower corrosion current. This behavior was interpreted considering the formation of a chromium oxide layer on the coating surface, dissolution and decomposition of smaller carbide particles and their surface enrichment with Cr due to C diffusion and dissolution into the matrix, and possible Ni, Cr, and Fe diffusion to coating/substrate interface. (c) 2006 the Electrochemical Society.

WC-CoCr coatings sprayed by high velocity oxygen-fuel (HVOF) flame on AA7050 aluminum alloy: electrochemical behavior in 3.5% NaCl solution

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

Resistência à corrosão das fases presentes em amálgamas dentários

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

Multi-spectroscopic monitoring of cisplatin-derived species delivery from ureasil polyether hybrid matrix

Driven by the challenges involved in the development of new advanced materials with unusual drug delivery profiles capable of improving the therapeutic and toxicological properties of existing cancer chemotherapy, the one-pot sol-gel synthesis of flexible, transparent and insoluble urea-cross-linked polyether-siloxane hybrids has been recently developed. In this one-pot synthesis, the strong interaction between the antitumor cisplatin (CisPt) molecules and the ureasil-poly(propylene oxide) (PPO) hybrid matrix gives rise to the incorporation and release of an unknown CisPt-derived species, hindering the quantitative determination of the drug release pattern from the conventional UV-Vis absorption technique. In this article, we report the use of an original synchrotron radiation calibration method based on the combination of XAS and UV-Vis for the quantitative determination of the amount of Pt-based molecules released in water. Thanks to the combination of UV-Vis, XAS and Raman techniques, we demonstrated that both the CisPt molecules and the CisPt-derived species are loaded into an ureasil-PPO/ureasil-poly(ethylene oxide) (PEO) hybrid blend matrix. The experimentally determined molar extinction coefficient of the CisPt-derived species loaded into ureasil-PPO hybrid matrix enabled the simultaneous time-resolved monitoring of each Pt species released from this hybrid blend matrix.

Electrochemical stability and corrosion resistance of Ti-Mo alloys for biomedical applications

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

Influence of HVOF parameters on the corrosion and wear resistance of WC-Co coatings sprayed on AA7050 T7

Thermal spray WC-based coatings are widely used in the aircraft industry mainly for their resistance to wear, reworking and rebuilding operations and repair of worn components on landing gear, hydraulic cylinders, actuators, propeller hub assemblies, gas turbine engines, and so on. The aircraft industry is also trying to use thermal spray technology to replace electroplating coatings such as hard chromium. In the present work, WC-Co coatings were built up on an AA 7050 aluminum alloy using high velocity oxygen fuel (HVOF) technology and a liquid nitrogen cooling prototype system. The influence of the spray parameters (standard conditions, W19S, increasing the oxygen flux, W19H, and also increasing the carrier gas flux, W19F) on corrosion, friction, and abrasive wear resistance were also studied. The coatings were characterized using optical (OM) and scanning electron (SEM) microscopy, and X-ray diffraction (XRD). The friction and abrasive wear resistance of the coatings were studied using Rubber Wheel and Ball on Disk tests. The electrochemical studies were conducted using open-circuit potential (E(oc)) measurements and electrochemical impedance spectroscopy (EIS). Differences among coated samples were mainly related to the variation of the thermal spray parameters used during the spray process. No significant differences were observed in the wear resistance for the coatings studied, and all of them showed a wear rate around 10 times lower than that of the aluminum alloy. The results of mass loss and wear rate were interpreted considering different mechanisms. Comparing the different spray parameters, the oxygen flux (higher flame temperature) produced the sample which showed the highest corrosion resistance in aerated and unstirred 3.5% NaCl solution. Aluminum ions were detected on the surface almost immediately after the immersion of samples W19S and W19F in chloride solution, showing that the electrolyte reached the substrate and galvanic corrosion probably occurred. For sample W19H, aluminum ions were not detected even after 120 min of immersion in NaCl solution. (C) 2008 Elsevier B.V. All rights reserved.

Cr3C2-NiCr and WC-Ni thermal spray coatings as alternatives to hard chromium for erosion-corrosion resistance

Cr3C2-NiCr and WC-Ni coatings are widely used for wear applications at high and room temperature, respectively. Due to the high corrosion resistance of NiCr binder, Cr3C2-NiCr coatings are also used in corrosive environments. The application of WC-Ni coatings in corrosive media is 14 not recommended due to the poor corrosion resistance of the (pure Ni) metallic matrix. It is well known that the addition of Cr to the metallic binder improves the corrosion properties. Erosion-corrosion performance of thermal spray coatings is widely influenced by ceramic phase composition, the size of ceramic particles and also the composition of the metallic binder. In the present work, two types of HVOF thermal spray coatings (Cr3C2-NiCr and WC-Ni) obtained with different spray conditions were studied and compared with conventional micro-cracked hard chromium coatings. Both as-sprayed and polished samples were tested under two erosion-corrosion conditions with different erosivity. Tungsten carbide coatings showed better performance under the most erosive condition, while chromium carbide coatings were superior under less erosive conditions. Some of the tungsten carbide coatings and hard chromium showed similar erosion-corrosion behaviour under more and less erosive conditions. The erosion-corrosion and electrochemical results showed that surface polishing improved the erosion-corrosion properties of the thermally sprayed coatings. The corrosion behaviour of the different coatings has been compared using Electrochemical Impedance Spectroscopy (EIS) and polarization curves. Total material loss due to erosion-corrosion was determined by weight loss measurements. An estimation of the corrosion contribution to the total weight loss was also given. (c) 2007 Elsevier B.V. All rights reserved.

Influence of cerium (IV) ions on the mechanism of organosilane polymerization and on the improvement of its barrier properties

In this work, the effect of cerium (IV) ammonium nitrate (CAN) addition on the polymerization of bis-[triethoxysilyl]ethane (BTSE) film applied on carbon steel was studied. The electrochemical characterization of the films was carried out in 0.1 mol L(-1) NaCl solution by open-circuit potential measurements, anodic and cathodic polarization curves and electrochemical impedance spectroscopy (EIS). Morphological and chemical characterization were performed by atomic force microscopy (AFM), contact angle measurements, infrared-spectroscopy, nuclear magnetic resonance and thermogravimetric analysis. The results have clearly shown the improvement on the protective properties of the Ce(4+) modified film as a consequence of the formation of a more uniform and densely reticulated silane film. A mechanism is proposed to explain the accelerating role of Ce(4+) ions on the cross-linking of the silane layer. (C) 2008 Elsevier Ltd. All rights reserved.

Effect of cerium (IV) ions on the anticorrosion properties of siloxane-poly(methyl methacrylate) based film applied on tin coated steel

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