45 research outputs found

    The corrosion and tribocorrosion resistance of PEO composite coatings containing α-Al2O3 particles on 7075 Al alloy

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    Plasma electrolytic oxidation (PEO) of 7075 Al alloy was carried out in silicate base electrolyte containing 200 nm diameter α-Al2O3 particles for producing composite coatings. The process was performed under a soft-sparking regime using a pulsed bipolar signal with several concentrations of α-Al2O3 particles. It was found that the incorporation of α-Al2O3 particles into the coating did not significantly alter the thickness and roughness of the coating. However, the α-Al2O3 particles were detected on surface of the composite coatings. Corrosion tests showed significant improvement in corrosion performance of the composite coatings due to the efficient pore blocking provided by α-Al2O3 particles, which enhances the barrier performance of both inner and outer layers of the coatings. However, the long-term EIS measurements showed that the performance of composite coatings becomes close to that of particle-free coating after 56 days of immersion in chloride containing solution. Tribocorrosion tests showed that adding 3 g·l−1 of α-Al2O3 particles to the electrolyte bath decreased the lost wear volume of the resulted coating from 30 to 10 mm3 (×10−3). Higher α-Al2O3 particles concentration (i.e. 7 g·l−1) showed detrimental effect on both corrosion and tribocorrosion performance of the coating

    Effects of pulse current mode on plasma electrolytic oxidation of 7075 Al in Na2WO4 containing solution: From unipolar to soft-sparking regime

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    Plasma electrolytic oxidation coatings were produced on 7075 Al alloy in a silicate based solution containing sodium tungstate using unipolar, usual bipolar and soft-sparking bipolar pulsed current regimes. X-ray diffraction proved that the coatings contain gamma alumina and metallic tungsten. EDS results showed that the tungsten content decreases with increasing the negative half cycle. Scanning electron microscopy showed that the pancake and volcano-like were dominant morphologies for the coatings produced by the unipolar and bipolar current regimes, respectively. Under unipolar current regime, a band of large pores is observed at the metal/coating interface, while they became discrete by applying the bipolar current regime and their population decreased significantly with increasing the negative half cycle. The coating produced by soft-sparking regime showed the highest corrosion resistance in chloride containing solution, resulting also very effective toward localized corrosion, due to a synergistic effect of W incorporation and employed waveform. Incorporation of tungsten resulted in the formation of hard coating (up to 1900 Hv) with dark appearance, therefore promising for thermal control applications

    Effect of Molybdate on Corrosion Performance of Oxide Coating Produced on 7075 Al Alloy Using PEO

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    In this research, plasma electrolytic oxidation (PEO) coatings were prepared on 7075 Al alloy in a silicate-based solution with Na2MoO4 additive using a unipolar waveform at constant current density. The coatings displayed micro-pores, micro-cracks, pancake-like and crater-like features, and also solidified molten oxide particles on the surface. The coatings were majorly composed of Al2O3 (γ, δ, and α), SiO2 (amorphous), and MoO3 phases, which confirms the incorporation of molybdenum in the case of additive-containing coatings. Molybdenum species were transported through cracks, channels, and micropores, as the ready access pathways into the coating and partly sealed the coating pores. The EIS technique was used to evaluate the long-term corrosion performance of the coatings up to 168 h of immersion in 3.5 wt.% NaCl solution. The results showed that the barrier action of the PEO coatings was highly enhanced by adding Na2MoO4 due to the higher resistance that alumina achieved to chlorine absorption and also its higher stability by the incorporation of MoO3. The coating formed in the presence of 5 g L−1 Na2MoO4 showed the highest thickness and the lowest porosity percent (15.15%), which provided the highest corrosion performance at long immersion times

    Tailoring the pseudocapacitive behavior of electrochemically deposited manganese-nickel oxide films

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    Manganese-nickel mixed oxide thin films were deposited by anodic electrodeposition on stainless steel substrate from an acetate solution using a potentiodynamic technique, at scan rate of 100 mV s-1 and room temperature. The effect of electrolyte pH, varied in the range from 4 to 7, on composition, morphology and capacitance behavior of oxide thin films was investigated. The nickel content in the oxide increased with increasing deposition pH, allowing to investigate the effect of the oxide composition on the capacitive behavior of as-grown manganese-nickel mixed oxides. Oxide films deposited from the electrolyte at pH 6, having a composition close to Ni0.10Mn0.90Ox showed the highest specific capacitance and the lowest charge transfer resistance. After annealing, the oxide had a complex structure of composite nature, consisting of intermixed amorphous and nanocrystalline phases. A birnessite type oxide with turbostratic disorder was identified as the major phase, in the presence of nickel hydroxide as a finely dispersed second phase. Annealing caused a drastic reduction of the charge transfer resistance and a limited increase of the specific capacitance, probably as the result of diverging effects on oxide properties, i.e. enhanced conductivity and porosity sintering. Cycle life testing of this material revealed a 25% increase of the specific capacitance over 5,000 cycles to a final value of 225 F g-1 (1 M Na2SO4, 50 mV s-1, 0.11 mg cm-2 mass loading)

    Effect of Anodic Deposition Parameters on Electrochemical Behavior and Microstructure of Mn-Ni Oxide As a Pseudocapacitive Electrode

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    Hybrid supercapacitors, or briefly pseudocapacitors, are an emerging class of energy storage devices, with the capability of providing both high power and energy density. In contrast to conventional electric double layer capacitors, which accumulate charge mostly through an electrostatic mechanism, pseudocapacitors utilize the pseudocapacitance arising from reversible Faradic reactions occurring at the electrode surface. Although various metal oxides have been investigated as active material for pseudocapacitors, greater attention has been given to manganese oxides. In recent years, also Mn-based binary oxides have been studied for pseudocapacitance, in particular, mixed oxides comprising Ni or Co as the other component. In the present work, Mn-Ni oxide thin films were deposited potentiodynamically at scan rate of 100 mVs-1, pH=7 and room temperature, on a stainless steel substrate. Undoubtedly, a survey of the literature shows that a systematic study on the effect of operating parameters on the properties of the mixed oxide thin films is still lacking. Accordingly, this work was undertaken with the aim of exploring the processing space for these oxides studying in particular the effects of the electrolyte Ni to Mn molar ratio, the deposition peak potential and the deposited mass on chemical composition, microstructure and capacitance behavior of Mn-Ni oxide thin films. The binary oxide deposits were characterized by energy dispersive X-ray spectroscopy (EDX) and scanning electron microscopy (SEM). The electrochemical behavior of the Mn-Ni oxide electrodes was studied by cyclic voltammetry (CV) at 5, 20, 50 and 100 mVs-1 and electrochemical impedance spectroscopy (EIS) in 1 M Na2SO4electrolyte. Expectedly, with increasing the Ni to Mn molar ratio in solution (from 0.1 to 10), the molar fraction of Ni in the oxide film was found to increase, resulting, on the one hand, in smoothing of the surface morphology and, on the other hand, in a change of the specific capacitance through a maximum of 145 Fg-1 at approximately 12% at Ni fraction and CV scan rate of 20 mVs-1. With further increase of the Ni fraction in the oxide to about 19% at, the specific capacitance started to decrease gradually. Changing the peak potential in the potentiodynamic deposition from +1.2 to +1.6 V vs. Ag/AgCl, the CV curves revealed a box-like shape for all values of the peak potential, while the capacitance showed a decreasing trend. EIS results revealed that charge transfer resistance increased with increasing peak potential and the lowest Rct was found for sample prepared at peak potential of 1.2 V vs. Ag/AgCl. The mass load per unit area of the film was controlled by the number of cycles. Finally, specific capacitance of 196 Fg-1 was obtained at scan rate of 5 mVs-1 for the Mn-Ni oxide film deposited potentiodynamically (5 cycles, 100 mVs-1, pH=7 and RT) in solution with Ni to Mn molar ratio of 2. At the high scan rate of 100 mVs-1, the specific capacitance was 135 Fg-1 showing good retention of the capacitance at high rate

    Electrochemically-induced TiO2 incorporation for enhancing corrosion and tribocorrosion resistance of PEO coating on 7075 Al alloy

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    7075 Al alloy was PEO-treated in a silicate based electrolyte containing 3 g l-1 potassium titanyl oxalate using unipolar and bipolar pulsed current waveforms. The coating formed by the bipolar waveform with the wider cathodic pulses showed volcano-like surface morphology with no evidence of large pores at the metal/coating interface. It revealed the highest corrosion performance due to the synergistic effect of TiO2 incorporation and structural/morphological features along with a better passivation behavior indicating no pitting susceptibility. For this coating, the tribocorrosion tests showed no potential drop during sliding under 1 N with the lowest volume loss of 0.022 mm3

    Nanosized Mn-Ni oxide thin films via anodic electrodeposition: A study of the correlations between morphology, structure and capacitive behaviour

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    The present study addresses the synthesis of manganese-nickel oxide thin films via potentiodynamic anodic electrodeposition as supercapacitor electrodes. We study in particular the effect of the deposition scan rate and of the Ni(II) to Mn(II) molar ratio in the deposition bath on the capacitive behaviour of mixed oxide electrodes. The increase of the nickel content in oxide thin films of composition NixMn1-xOy (with x in the range from 0 to 0.17) results in the increase of specific capacitance up to a maximum for about 10 at% Ni. The deposition scan rate affects the capacitive behaviour of mixed oxide electrodes through its effects on layer morphology and surface structure. In particular, thin film electrodes at about 10 at% Ni show a maximum in the specific capacitance for deposition scan rate of 600 mV s-1, which is shown to be related to the attendant modifications in surface morphology and topography. After annealing at 200 °C, 6 h, partial crystallization of the amorphous structure of the as-grown mixed oxide takes place with formation of dispersed nanocrystalline domains. The annealed electrode at 10 at% Ni, with mass loading of 0.30 mg cm-2, show the highest specific capacitance (250 F g-1, at 0.1 A g-1), and specific energy and power as high as 34.5 Wh kg-1 (at 50 W kg-1), and 4.3 kW kg-1 (at 15.7 Wh kg-1). Mixed oxide of the same composition and mass loading reveal a 122% capacitance retention after 10,000 cycles in 1 M Na2SO4 at 20 A g-1

    Study on the Effect of Annealing Process on Microstructure and Electrochemical Behavior of the Binary Mn-Ni Nano-Oxide Pseudocapacitor Synthesized by Anodic Deposition

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    In the present investigation, Mn-Ni binary nano-oxide was deposited by potentiodynamic method on stainless steel at room temperature and the effect of annealing process (at 200 oC for 6 h) on microstructure and electrochemical performance of the synthesized pseudocapacitor was studied. The results showed the significant effect of annealing process on increasing the capacitance and decreasing the charge transfer resistance of the electrode. Field Emission Scanning Electron Miscroscopy (FESEM) images depicted interconnected and random nano-flakes in the oxide film microstructure. Moreover, a partially crystallized structure consisting disorder hexagonal birnessite type phase was formed upon annealing in the deposited oxide film with about 10 %at Ni in composition. Based on the galvanostatic charge-discharge plots, the highest specific capacitance (384 F g-1) and specific energy (53 Wh kg-1) were found at specific current of 0.1 A g-1 for the annealed oxide electrode. Finally, cycle life test results at specific current of 10 A g-1 showed an excellent cyclability and an increase of about 23% in specific capacitance of synthesized pseudocapacitor after 5000 charge-discharge cycles in 1 M Na2SO4

    Effects of pulse current mode on plasma electrolytic oxidation of 7075 Al in KMnO4containing solution

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    Plasma electrolytic oxidation of 7075 Al alloy was performed in alkaline silicate electrolyte containing KMnO4as an additive using unipolar (U) and bipolar pulsed current modes (B1 and B2). The coating grown using the bipolar current with longer cathodic pulse time (B2) revealed a more dense foam-like surface morphology with fewer volcano areas providing higher thickness, which is mainly raised by reduction in discharge intensity. Also, a lower concentration of electrolyte elements (Si and Mn) was incorporated into the coating providing a brighter appearance. EIS results showed very high inner layer resistances for the coatings indicating this layer controls the overall corrosion performance of the coatings. In this way, the highest inner layer resistance along with very low value of constant phase element was achieved for the coating produced by B2, which is an indication for its lower porosity and higher thickness. Also, the more noble corrosion potential and lower passive current density observed for this coating in potentiodynamic polarization test confirms its stronger barrier effect against the chloride ingression where its corroded surface after long-term EIS test showed no significant damage. The lower penetration depth and subsequently the higher hardness values were achieved for the coatings produced by B2
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