Polypyrrole films on nickel-plated copper

Polypyrrole (PPy) film was synthesized on nickel-plated copper electrodes, from monomer containing 0.2 M ammonium oxalate solution. The thickness of galvanostatically deposited nickel layer was 2 μm, while 0.80 μm thick polymer film was obtained by using cyclic voltammetry technique. The protective behavior of PPy modified nickel coating has been investigated, against copper corrosion in 3.5% NaCl solution. For this aim, ac impedance spectroscopy, the anodic polarization curves and open circuit potential–time (E_ocp–t) diagrams were utilized. It was shown that PPy modified nickel coating could provide important protection to copper for considerable periods, in such aggressive medium. The thin polymer film constituted a physical barrier on top of nickel layer against the attack of corrosive environment for a certain period. Also, it was found that the thin PPy film could increase the protection efficiency and lifetime of nickel coating, by its catalytic behavior on formation of NiO layer.     

In situ photoelectrochemistry and Raman spectroscopic characterization on the surface oxide film of nickel electrode in 30 wt.% KOH solution

The oxide films of nickel electrode formed in 30 wt.% KOH solution under potentiodynamic conditions were characterized by means of electrochemical, in situ PhotoElectrochemistry Measurement (PEM) and Confocal Microprobe Raman spectroscopic techniques. The results showed that a composite oxide film was produced on nickel electrode, in which aroused cathodic or anodic photocurrent depending upon polarization potentials. The cathodic photocurrent at −0.8 V was raised from the amorphous film containing nickel hydroxide and nickel monoxide, and mainly attributed to the formation of NiO through the separation of the cavity and electron when laser light irradiates nickel electrode. With the potential increasing to more positive values, Ni₃O₄ and high-valence nickel oxides with the structure of NiO₂ were formed successively. The composite film formed in positive potential aroused anodic photocurrent from 0.33 V. The anodic photocurrent was attributed the formation of oxygen through the cavity reaction with hydroxyl on solution interface. In addition, it is demonstrated that the reduction resultants of high-valence nickel oxides were amorphous, and the oxide film could not be reduced completely. A stable oxide film could be gradually formed on the surface of nickel electrode with the cycling and aging in 30 wt.% KOH solution.     

Nature of the passive film on nickel

The passive film formed anodically on nickel in borate buffer solution in both the passive and transpassive regions is found to be p-type in electronic character, corresponding to a preponderance of metal vacancies (over oxygen vacancies and nickel interstitials) in the barrier layer. However, at high anodic potentials, some n-type character was detected by Mott-Schottky analysis, which is probably due to the presence of free charge carriers (electrons) from the evolution of oxygen and/or the oxidative ejection of Ni³⁺ at the barrier layer/outer layer interface. The p-type character of the film is consistent with the diagnostic criteria obtained from the Point Defect Model for a passive film, in which the majority defect in the NiO barrier layer is the metal vacancy. The transpassive state is postulated to comprise a thick, porous oxide film on the surface, with the current probably being due to the oxidative ejection of Ni³⁺ species from the barrier layer and oxygen evolution within the pores, or both.     

Evaluation of electroactive intermediate states in anodic O2 evolution at chemically formed nickel oxide: Comparison with behaviour at nickel metal anodes

The behaviour of the kinetically involved intermediate states arising in the electrocatalysis of anodic oxygen evolution at chemically formed, high-area nickel oxide (NiO·OH) films on nickel metal as substrate is examined by means of analysis of potential (V) decay transients, following interruption of anodic polarization currents at various overpotentials. The potential decay behaviour is treated in terms of the dependence ofV(t) on log (time,t), and of ln (–dV/dt) as f[V(t)]. The pseudocapacitance associated with the potential-dependence of the coverage or surface density of the overpotential-deposited species involved as intermediates in the reaction at the oxide electrode surface is evaluated jointly from the potential decay and Tafel polarization behaviour, following procedures developed recently.In anodic O₂ evolution on oxide surfaces, such as NiO·OH, the intermediate states in the kinetics of the reaction are to be identified as OH or O species coupled with potential-dependent Ni(III) and Ni(IV) oxidation states of nickel, and the surface density of these states can be evaluated experimentally.The results obtained for anodic O₂ evolution on the chemically formed nickel oxide films are compared with the behaviour at anodically formed thin oxide films on nickel metal.     

Electrooxidation of alcohols at a nickel oxide/multi-walled carbon nanotube-modified glassy carbon electrode

Electrocatalytic oxidation of methanol and some other primary alcohols on a glassy carbon electrode modified with multi-walled carbon nanotubes and nano-sized nickel oxide (GCE/MWNT/NiO) was investigated by cyclic voltammetry and chronoamperometry in alkaline medium. The results were compared with those obtained on a nickel oxide-modified glassy carbon electrode (GCE/NiO). Both the electrodes were conditioned by potential cycling in the range of 0.1–0.6 V versus Ag/AgCl in a 0.10 M NaOH solution. The effects of various parameters such as scan rate, alcohol concentration, thickness of NiO film, and real surface area of the modified electrodes were also investigated and compared. It was found that the GCE/MWNT/NiO-modified electrode possesses an improved electrochemical behavior over the GC/NiO-modified electrode for methanol oxidation.     

Effect of NiO on the Phase Stability and Microstructure of Yttria-Stabilized Zirconia

Nickel oxide (NiO) was screen printed onto the surfaces of 3 and 8 mol% yttria-stabilized zirconia (YSZ) dense pre-fired substrates and then heat treated at temperatures from 1350° to 1550°C. The effect of NiO was dependent on the yttria content of the substrate. In 3 mol% YSZ, it was found to alter the phase composition from predominantly tetragonal with a small amount of cubic phase to one consisting of approximately equal amounts of cubic and monoclinic phase. The cubic grains were much larger than the monoclinic ones and contained more nickel. Furthermore, nickel was observed to migrate through the thickness of the tile, a distance of approximately 200 μm. In the 8 mol% YSZ substrates, the phase composition was unaltered, although large grains developed under the printed NiO layer and the nickel migration was confined to the extent of these large grains.     

Role of oxygen vacancies on the energy storage performance of battery-type NiO electrodes

In this study, the influence of the surface oxygen vacancies on the energy storage performance of electrodes based on nickel oxide (NiO) nanoparticles was investigated. NiO samples were synthesized by three facile and low-cost syntheses routes: nitrate calcination, citrate, and combustion methods. The concentration of surface defects in NiO powders was determined using XPS analyses, which showed a higher amount of oxygen vacancies for the sample obtained by nitrate calcination. According to the cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) curves, NiO-based electrodes were classified as battery-like. CV results suggest that redox reactions are diffusion-controlled processes with a faster diffusion rate for the sample obtained by the nitrate calcination method. This is in accordance with the GCD and electrochemical impedance spectroscopy (EIS) results, with higher specific capacity and higher electrical conductivity (lower equivalent series resistance) for the sample obtained by nitrate calcination. The results indicate that oxygen vacancies play an important role in the electrochemical performance of battery-type NiO electrodes.     

Corrosion under a porous layer: A porous electrode model and its implications for self-repair

A one-dimensional mathematical model for the corrosion of a metal surface under a porous layer (often an oxide layer) is presented using porous electrode theory. The model allows one to predict the rates of corrosion in a metallic system where oxygen reduction is the only cathodic reaction which occurs on the surfaces of both the metal and the porous oxide layer albeit at different rates. Thus the model simulates the scenario where the porous layer residing on the metal surface competes with or complements the oxygen reduction reaction happening on the metal surface. The study finds that a large thickness, low porosity, low oxide electrical conductivity, poor oxygen reduction on the porous layer, and high specific contact resistivity of the metal–oxide lead to poor spatial separation of the anodic and cathodic reactions and hence encourage self-repair. In particular the metal–oxide contact potential and the oxygen reduction rates on the oxide surface are shown to have profound implications for self-repair strategies for corrosion mitigation.     

Nb effect in the nickel oxide-catalyzed low-temperature oxidative dehydrogenation of ethane

A method for the preparation of NiO and Nb–NiO nanocomposites is developed, based on the slow oxidation of a nickel-rich Nb–Ni gel obtained in citric acid. The resulting materials have higher surface areas than those obtained by the classical evaporation method from nickel nitrate and ammonium niobium oxalate. These consist in NiO nanocrystallites (7–13 nm) associated, at Nb contents >3 at.%., with an amorphous thin layer (1–2 nm) of a niobium-rich mixed oxide with a structure similar to that of NiNb₂O₆. Unlike bulk nickel oxides, the activity of these nanooxides for low-temperature ethane oxidative dehydrogenation (ODH) has been related to their redox properties. In addition to limiting the size of NiO crystallites, the presence of the Nb-rich phase also inhibits NiO reducibility. At Nb content >5 at.%, Nb–NiO composites are thus less active for ethane ODH but more selective, indicating that the Nb-rich phase probably covers part of the unselective, non-stoichiometric, active oxygen species of NiO. This geometric effect is supported by high-resolution transmission electron microscopy observations. The close interaction between NiO and the thin Nb-rich mixed oxide layer, combined with possible restructuration of the nanocomposite under ODH conditions, leads to significant catalyst deactivation at high Nb loadings. Hence, the most efficient ODH catalysts obtained by this method are those containing 3–4 at.% Nb, which combine high activity, selectivity, and stability. The impact of the preparation method on the structural and catalytic properties of Nb–NiO nanocomposites suggests that further improvement in NiO-catalyzed ethane ODH can be expected upon optimization of the catalyst.     

Anion incorporation and its effect on the dielectric constant and growth rate of zirconium oxides

Mechanically polished zirconium electrodes were potentiodynamically polarized in phosphate buffer solutions of various pH values and in 0.5 lvl NaOH. The results show that the shape of the I-E curves is independent of the solution pH. At relatively low scan rates, oxygen gas evolution was observed. The oxide film thickness was calculated from the values of the charge consumed in the anodic process assuming 100% current efficiency for oxide formation below oxygen evolution (lower values for the current efficiency are assumed for potentials above oxygen evolution). Capacitance measurements, together with the calculated oxide thickness, were used to estimate values for the dielectric constant of the oxide. Two different values of the dielectric constant were obtained for the oxides formed in the range of potential below and above oxygen evolution. Also, higher dielectric constant values were obtained with increasing solution pH. Anion incorporation was assumed to increase the conductivity of the oxide films and, hence, decrease the dielectric constant. A two-layer structure is proposed for the anodically formed oxide on zirconium in aqueous solutions; an anion-free layer near the metal and an outer layer containing the incorporated anions.     

汽车用铝合金阳极氧化及双重封闭工艺的研究

对汽车用2024铝合金进行了硫酸阳极氧化处理,并使用硫酸镍结合铬酸钾的双重封闭技术对阳极氧化膜进行了封闭处理。结果表明:在2024铝合金表面制备的阳极氧化膜属于典型的多孔膜。经过硫酸镍一次封闭处理后,大量镍的氢氧化物填充于膜孔内,有效地降低了阳极氧化膜的自腐蚀电流密度。经过铬酸钾二次封闭处理后,铬酸镍进一步覆盖在膜孔表面,大大提高了阳极氧化膜的均匀性和致密性。经过双重封闭处理后,阳极氧化膜的阻抗明显增大,耐蚀性大大提高。     

Phytoextract assisted hydrothermal synthesis of ZnO–NiO nanocomposites using neem leaves extract

This work represents the synthesis of zinc oxide nanorods, nickel oxide nanoparticles, and zinc oxide-nickel oxide nanocomposites by combining Neem leave extract with hydrothermal synthesis. Five samples were prepared by green synthesis which is based on Neem leaves aqueous extract followed by hydrothermal treatment at 250 °C for 2.5 h. The five prepared samples are: 100% NiO (N100), 75% NiO: 25% ZnO (Z25-N75), 50% NiO: 50% ZnO (Z50-N50), 25% NiO: 75% ZnO (Z75-N25), and 100% ZnO (Z100). The prepared nanoparticles and nanocomposites were characterized by FTIR, XRD, SEM, and TEM. The XRD results show that the ZnO formed as a hexagonal wurtzite phase and NiO as a cubic phase. The microstructure of the formed samples is versatile with nanorods ZnO and spherical NiO. The nanocomposites microstructure appears as a heterostructure of both oxides with NiO particles on the surface of ZnO rods. The TEM confirms the nanosize and the crystallinity of samples.     

Temperature-programmed reduction of NiOWO3/Al2O3 Hydrodesulphurization catalysts

Temperature-programmed reduction patterns are reported of NiO/Al₂O₃, WO₃/Al₂O₃, and NiOWO₃/Al₂O₃ catalysts, and of bulk oxides relevant to these catalysts. At loadings below 10% NiO and 19% WO3 nickel and tungsten are present as disperse species and no bulk oxides are found on the support. Tungsten forms a stable monolayer species which is extremely difficult to reduce. At high temperatures of reduction tungsten metal is formed without the intermediate formation of WO₂. Several nickel species were detected in the supported catalysts, and their characters and amounts depend on the loading and the temperature of calcination. After calcination at low temperatures and at low loadings (2% NiO) nickel is incorporated in the surface layers of the support; at higher loadings a NiO like species is formed which is more difficult to reduce than bulk NiO because of the interaction with the aluminium ions of the support. A high temperature of calcination favours the formation of a diluted spinel phase at the expense of the surface phases. In NiOWO₃/Al₂O₃ catalysts a fraction of nickel is present in a mixed NiWOAl phase which is formed by incorporation of nickel in a tungsten containing surface layer. At high temperatures of calcination some disperse NiWO₄ is formed. It is shown that there are two causes for a strong interaction between nickel species and the support: incorporation of nickel ions in the surface layers of the support during impregnation, and solid-state diffusion during calcination of the catalysts. The nickel containing species which are the precursor to the active phases in sulfided HDS catalysts are identified as the nickel species in the surface layers of the support in NiO/Al₂O₃ samples, and the NiWOAl phase in NiOWO₃/Al₂O₃ catalysts.     

INHIBITION OF ACIDIC AND PITTING CORROSION OF NICKEL USING NATURAL BLACK CUMIN OIL

The inhibition effect of natural black cumin oil on the corrosion of nickel in 0.1 M HCl solution was studied using galvanostatic and potentiodyanmic anodic polarization techniques. It was found that the inhibition efficiency increased with an increase in the inhibitor concentration of this oil. The inhibitive action of black cumin oil was attributed to the adsorption on metal surface. The adsorbed layer acts as a barrier between the metal surface and aggressive solution, leading to a decrease in the corrosion rate. The adsorption process follows the Langmuir adsorption isotherm. It was found also that black cumin oil provides good protection to nickel against pitting corrosion in sodium chloride solutions.     

The study of hydrogen electrosorption in layered nickel foam/palladium/carbon nanofibers composite electrodes

In the present work, the process of hydrogen electrosorption occurring in alkaline KOH solution on the nickel foam/palladium/carbon nanofibers (Ni/Pd/CNF) composite electrodes is examined. The layered Ni/Pd/CNF electrodes were prepared by a two-step method consisting of chemical deposition of a thin layer of palladium on the nickel foam support to form Ni/Pd electrode followed by coating the palladium layer with carbon nanofibers layer by means of the CVD method. The scanning electron microscope was used for studying the morphology of both the palladium and carbon layer. The process of hydrogen sorption/desorption into/from Ni/Pd as well as Ni/Pd/CNF electrode was examined using the cyclic voltammetry method. The amount of hydrogen stored in both types of composite electrodes was shown to increase on lowering the potential of hydrogen sorption. The mechanism of the anodic desorption of hydrogen changes depending on whether or not CNF layer is present on the Pd surface. The anodic peak corresponding to the removal of hydrogen from palladium is lower for Ni/Pd/CNF electrode as compared to that measured for Ni/Pd one due to a partial screening of the Pd surface area by CNF layer. The important feature of Ni/Pd/CNF electrode is anodic peak appearing on voltammetric curves at potential ca. 0.4 V more positive than the peak corresponding to hydrogen desorption from palladium. The obtained results showed that upon storing the hydrogen saturated Ni/Pd/CNF electrode at open circuit potential, diffusion of hydrogen from carbon to palladium phase occurs due to interaction between carbon fibers and Pd sites on the nickel foam support.     

Characterisation and behaviour of Ti/TiO2/noble metal anodes

The morphology, composition and the electrical and electrochemical behaviour of the anodic microporous layer, prepared by the galvanostatic anodisation of Ti after sparking, followed by galvanostatic deposition of Pt or Ir have been investigated. These electrodes are proposed to function as dimensionally stable anodes (DSAs). For Ti/TiO₂/Pt electrodes, Pt is deposited within some of the micropores of the oxide film. In contrast, for Ti/TiO₂/Ir, the metal is deposited preferentially on the top surface. This difference is thought to result from the position of the metal deposition potential with respect to the flat band potential of n-TiO₂. Optical imaging of both types of DSA suggests that only a few sites on the surface are responsible for electron exchange at the DSA-electrolyte interface. C-AFM measurements of Ti/TiO₂/Pt samples subjected to long-term anodic polarisation, suggest that the Ti-noble metal contact is progressively insulated by thickening of the TiO₂ barrier layer, promoting passivation of the DSA. For Ir coated anodes, catalytic activity is directly related to the presence of Ir and to the stability of the catalytic oxide layer. Under Cu electrowinning conditions, the electrochemically formed hydrated Ir oxide was found to be catalytically less stable, than the iridium oxide film subjected to a heat treatment.     

Effect of chloride concentration range on the corrosion resistance of Cu–xNi alloys

The anodic behaviour of Cu–xNi alloys and Cu and Ni metals was studied in slightly alkaline solutions containing Cl–-ions in the concentration range from 0.01 to 2.0moldm–3. The morphology and composition of the surface films formed by anodic polarization were analysed by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). On the basis of quasi-potentiodynamic polarization data, Ec against cNaCl diagrams were constructed, where Ec is the critical pitting potential. These diagrams allow the determination of areas where the materials are susceptible to localized pitting attack. A critical chloride concentration (ccrit) exists below which the resistance to localized corrosion increases with decreasing nickel content and above which it increases with increasing nickel content. This effect is connected with the change in the corrosion resistance observed for the pure metal constituents, i.e., copper and nickel as a function of chloride concentration. The kinetic parameters of pitting corrosion of Cu–xNi alloys reflect the specific properties of both elements and suggest that an increase in Ni content above 40% would not have a significant effect on the corrosion resistance of Cu–xNi alloys.     

INHIBITION OF THE CORROSION OF NICKEL AND ITS ALLOYS BY NATURAL CLOVE OIL

The corrosion behavior of nickel, Inconel 600, and Inconel 690 in different concentrations of HCl solutions and its inhibition by clove oil was studied using potentiostatic polarization measurements. As the acid concentration increases, the rate of corrosion increases, indicating that HCl accelerates the dissolution of nickel and its alloys. The inhibition efficiency of the clove oil was found to increase with increase of its concentration. The inhibitive action of this oil was discussed in view of adsorption onto the metal surface. The adsorbed layer acts as a barrier between the metal surface and aggressive solution, leading to a decrease in corrosion rate. The adsorption process follows Langmuir adsorption isotherms. It was found that the clove oil provides good protection to nickel and its alloys against pitting corrosion in chloride-containing solution using potentiodynamic anodic polarization techniques.     

Corrosion of dissimilar alloys: Electrochemical noise

A new approach for interpreting the electrochemical noise generated by freely corroding electrodes is presented. For a single electrode, with well-defined anodic and cathodic regions, it is proposed that the instantaneous values of the corrosion current and open circuit potential are functions of the time-invariant potential difference between the anodic and cathodic reactions and the time-dependent impedances associated with the anodic and cathodic reactions. The fluctuations in the values of anodic and cathodic impedances are determined by the interaction between the aggressive environment and the oxide, hydroxide or adsorbed surface layer covering the anodic and cathodic regions; the instantaneous values of impedances modulate the corrosion current. The mathematical implications of these assumptions are discussed and the results are compared with the traditional approach, based on time-dependent current sources acting on constant impedances. Subsequently, the findings for a single electrode are transferred to two dissimilar electrodes and an experimental technique that enables the estimation of the time evolution of anodic and cathodic resistances for each of the dissimilar electrodes is presented.     

镀金焊盘酸蚀缺损探讨

PCB板内表面涂覆为"电金+化金"是比较新颖的工艺,但在生产过程中发现有镀金焊盘缺损的问题。本文通过分析不同金镍厚组合的镀金焊盘在酸蚀中的抗蚀能力,得出金厚达到一定厚度时,致密的金层会成为阴极性镀层,加速蚀刻作为阳极性镀层的镍层,其速度至少加快2倍。利用这一规律,重新定义了合理的金厚范围,优化了酸蚀中保护镀金盘的干膜尺寸。