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51.
The electrodeposition and dissolution of yttrium-hexacyanoferrate [YHCNFe(II)] were investigated by electrochemical quartz crystal microbalance technique (EQCM). The electrodeposition was carried out by potential cycling or stepping from solutions of Y(NO3)3 and K3[FeIII(CN)6] of different concentrations. The ratio of the reactants was also varied. No deposition was found in dilute solutions (c < 10−3 mol dm−3). The increase of concentrations led to an intense deposition of YHCNFe(II) in the course of reduction of [FeIII(CN)6]3−. At high concentrations of the reactants a coagulation deposition of YHCNFe(III) at open-circuit has also been detected. During the reduction the first phase is the nucleation which requires saturation or oversaturation in respect to the reacting species near the gold surface. The growth phase is much faster than the formation of nuclei, and its rate depends on the concentration and the concentration ratio of the species. The composition of the deposits has been determined by total reflection X-ray fluorescence (TXRF) spectrometry. From the molar ratio of atomic constituents (K, Y and Fe) of the slightly soluble deposit (solubility: 5 × 10−5 mol dm−3) formed after reduction of Fe(III) a formula K0.46Y1.18[FeII(CN)6] can be derived. This value is in good accordance with the molar mass calculated from the results of EQCM experiments which also revealed that the deposit contains ca. 2 mol H2O/mol YHCNFe(II). The solubility of YHCNFe(III) is substantially higher (s = 2 × 10−3 mol dm−3), and according to the results of TXRF measurements, its composition is Y[FeIII(CN)6]. The reoxidation of YHCNFe(II) takes place in two steps. The first one is a partial oxidation which is accompanied by the desorption of K+ ions from the layer. During further oxidation a fast dissolution occurs due to the high solubility of YHCNFe(III). 相似文献
52.
Carbon materials are often used as catalyst supports, and for catalysts in electrodes of a polymer electrolyte fuel cell, carbon black has been used. Recently, it was found, however, that activated carbon could replace carbon black and besides, significantly improve the activity of the electrode catalyst layer for oxygen reduction. In the present study, to optimize the pore structure of activated carbon for further activity improvement, the influence of the pore structure on the activity was investigated using activated carbon of various specific surface areas and mean pore diameters. A catalyst layer was formed from activated carbon loaded with platinum and a polymer electrolyte. The activity of the layer was measured in an oxygen-saturated perchloric acid solution, supporting the layer on a rotating glassy carbon disk electrode. We found that increases in the specific surface area and mean pore diameter increased the activity and that the latter was more effective than the former mainly due to the enhanced mass-transfer in the pores; the catalyst layer formed from activated carbon with the largest mean pore diameter was the most active. Unless pores excessively develop and lose connections between particles, a large pore diameter is therefore desired for the fuel cell electrodes. 相似文献
53.
Preliminary evaluation of the anticorrosive properties of aircraft coatings by electrochemical methods 总被引:5,自引:0,他引:5
L. B. Reynolds R. Twite M. Khobaib M. S. Donley G. P. Bierwagen 《Progress in Organic Coatings》1997,32(1-4):31-34
Strict regulations concerning the content of volatile organic compounds (VOCs) and heavy metals (Cr6+) in aircraft coating systems have increased the economic burden of the United States Air Force (USAF) in the area of coating maintenance. To this end, it is critical to have methods to characterize new coating systems in such a manner that the data can be used to predict accurately and reliably the expected lifetime of the coatings in service. Electrochemical noise method (ENM) and electrochemical impedance spectroscopy (EIS) are two techniques used to monitor extent and rate of corrosion. The USAF is currently employing these methods in order to supplement data acquired from traditional salt-spray methods. ENM and EIS are used to evaluate each component of the coating system and its contribution to corrosion prevention. Preliminary evaluations of an aircraft coating system on aluminum substrate (Al 2024-T3) produces resistance noise values of 106 to 107 Ω/cm2. It is hoped that these results will form the basis of coatings that give increased USAF fleet service life and reduction in maintenance manpower and materials costs. 相似文献
54.
Polyaniline emeraldine base/epoxy resin (EB/ER) coating was investigated for corrosion protection of mild steel coupled with copper in 3.5% NaCl solution. EB/ER coating with 5-10 wt% EB had long-term corrosion resistance on both uncoupled steel and copper due to the passivation effect of EB on the metal surfaces. During the 150 immersion days, the impedance at 0.1 Hz for the coating increased in the first 1-40 days and subsequently remained constant above 109 Ω cm2, whereas that for pure ER coating fell below 106 Ω cm2 after only 30 or 40 days. Immersion tests on coated steel-copper galvanic couple showed that EB/ER coating offered 100 times more protection than ER coating against steel dissolution and coating delamination on copper, which was mainly attributed to the passive metal oxide films formed by EB blocking both the anodic and cathodic reactions. Salt spray tests showed that 100 μm EB/ER coating protected steel-copper couple for at least 2000 h. 相似文献
55.
Takuya Goto 《Electrochimica acta》2005,50(6):1283-1288
Electrochemical formation of aluminum nitride was investigated in molten LiCl-KCl-Li3N systems at 723 K. When Al was anodically polarized at 1.0 V (versus Li+/Li), oxidation of nitride ions proceeded to form adsorbed nitrogen atoms, which reacted with the surface to form AlN film. The obtained nitrided film had a thickness of sub-micron order. The obtained nitrided layer consisted of two regions; the outer layer involving AlN and aluminum oxynitride and the inner layer involving metallic Al and AlN. When Al electrode was anodically polarized at 2.0 V, anodic dissolution of Al electrode occurred to give aluminum ions, which reacted with nitride ions in the melt to produce AlN particles (1-5 μm of diameter) of wurtzite structure. 相似文献
56.
Two zinc-rich powder coatings are applied onto phosphatised steel substrate and are studied using electrochemical impedance spectroscopy (EIS). Measurements are performed before (dry experiment) and during immersion in artificial sea water. Before immersion, EIS spectra show that percolation threshold is not attained for coating A, while coating B presents an effective percolation. In this latter case, and in order to account for the distribution of the zinc particles within the coating described as isolated, semi-isolated and percolant grains, a distributed transmission line model is proposed. When panels are immersed, the model is modified due to the electrolyte penetration through the coating, in particular with the introduction of an ionic resistance. However, it is shown that EIS spectra are not significantly modified when this ionic resistance is changed. 相似文献
57.
For the first time, graphite fibers have been electrochemically intercalated with Br− that have the same structure and properties as those intercalated from vapor phase Br2. This was accomplished by intercalating pitch-based Thornel® K-1100 graphite fibers at low temperature (near 0 °C) and high currents (2 A) for long times (6 h). The mechanism appears to be that Br− is oxidized to aqueous Br2 which, when sufficient local concentration builds up, intercalates the fiber. This was confirmed by intercalating K-1100 fiber in a saturated aqueous Br2 solution without passing an electrical current. The applied voltage does apparently lower the activation energy of the reaction as evidenced by the observation that P-120 and P-100 fibers will not intercalate in aqueous Br2 unless a voltage is applied. 相似文献
58.
Electrochemical characterization of 8-hydroxyquinoline-5-sulphonate/aluminium(III) aqueous solutions
Denis Badocco Annalisa Dean Valerio Di Marco Paolo Pastore 《Electrochimica acta》2007,52(28):7920-7926
8-Hydroxyquinoline-5-sulphonate/Al(III) aqueous solutions were studied both by potentiometric titrations and voltammetric measurements, in order to obtain the number, the stoichiometry and the stability constants of the complexes formed at equilibrium, and to evaluate the redox and (electro)kinetic properties of the free ligand and of the metal/ligand complexes. The complexes formed in 0.2 m (Na)Cl aqueous solution (stability log beta values ± standard deviation) are AlL+ (8.95 ± 0.05), AlL2− (17.43 ± 0.03) and AlL33− (24.58 ± 0.05), where “L” denotes the free ligand in the completely deprotonated form (L2−, pKa1 = 3.910 ± 0.008, pKa2 = 8.319 ± 0.004). AlL33− is the predominant Al(III) species in a very wide range of pH, metal and ligand concentrations and metal-to-ligand ratios. The free ligand shows an oxidation wave at 0.62 V versus SCE. The proposed oxidation mechanism includes a first reversible one-electron oxidation of the ligand, followed by a coupling reaction and by a second reversible one-electron oxidation, and finally by a decomposition reaction. The addition of Al(III) lowers the intensity of the oxidation wave due to the formation of the redox-inactive complex AlL33−. A residual low signal was attributed to the free ligand produced by the complex dissociation, AlL33− = AlL2− + L2−. All the kinetic parameters involved in the ligand oxidation and in the complex disruption were calculated on the basis of the agreement between experimental and simulated linear sweep and cyclic voltammetries. Correctness of the mechanisms proposed was further confirmed “a posteriori” by the agreement between potentiometric and linear sweep voltammetric results. The low residual signal observed in the presence of fully formed complex was attributed to the free ligand produced by the complex dissociation, having a kinetic constant estimated 0.2 s−1. 相似文献
59.
Laurence J. Hardwick Matthias Hahn Michael Holzapfel Hilmi Buqa Petr Novák 《Electrochimica acta》2006,52(2):675-680
An initial Raman study on the effects of intercalation for aprotic electrolyte-based electrochemical double-layer capacitors (EDLCs) is reported. In situ Raman microscopy is employed in the study of the electrochemical intercalation of tetraethylammonium (Et4N+) and tetrafluoroborate (BF4−) into and out of microcrystalline graphite. During cyclic voltammetry experiments, the insertion of Et4N+ into graphite for the negative electrode occurs at an onset potential of +1.0 V versus Li/Li+. For the positive electrode, BF4− was shown to intercalate above +4.3 V versus Li/Li+. The characteristic G-band doublet peak (E2g2(i) (1578 cm−1) and E2g2(b) (1600 cm−1)) showed that various staged compounds were formed in both cases and the return of the single G-band (1578 cm−1) demonstrates that intercalation was fully reversible. The disappearance of the D-band (1329 cm−1) in intercalated graphite is also noted and when the intercalant is removed a more intense D-band reappears, indicating possible lattice damage. For cation intercalation, such irreversible changes of the graphite structure are confirmed by scanning electron microscopy (SEM). 相似文献
60.
The aim of this study was to clarify whether the C3A content of cement had a significant effect on electrochemical chloride extraction (ECE) treatment efficiency. It is known that a higher C3A content in a cement gives it superior chloride complexing ability resulting in the formation of an “insoluble” calcium chloro aluminate compound.ECE was applied using cylindrical specimens made from concrete containing two levels of C3A (4.3% and 9.05%). Specimens were 5 cm in diameter and 10 cm in height. Steel was placed in the axial direction with an embedded length of 7 cm. These specimens were immersed in an NaCl solution and dried in a stream of air at 40 °C for 10 months. The corrosion was monitored by half-cell potential and polarization resistance measurements. After steel depassivation, ECE was applied for 20, 30, 40 and 50 days using a constant current density of 1 A/m2 of steel. At the end of the treatment, the specimens were maintained at 20 °C and 70% RH in order to observe the evolution of the steel (electrochemical measurements).The results show that, after 30 days of treatment, the chloride content remained constant in the specimen. This was probably due to OH− ion formation on the steel. The OH− ions “contribute” to the current transport, decreasing the ECE efficiency. Concerning the C3A content, ECE efficiency was slightly affected by C3A because only a part of the bound chloride ions was released. From the point of view of corrosion, half-cell potential showed a shift in the positive direction, indicating little corrosion activity at 20 °C and 70% RH. However, polarization resistance measurements showed that 2 months post treatment corrosion rates were significant, although the corrosion rate decreased from 6 μA/cm2 to 2.5 μA/cm2. 相似文献