Corrosion behaviors of Cr2AlC/α-Al2O3 composites in 3.5 wt. % NaCl aqueous solution

Cr₂AlC and its composites containing α-Al₂O₃ (6.1 and 15.2 wt %) were prepared by hot pressing and their corrosion behaviors in air-saturated 3.5 wt % NaCl aqueous solution were investigated by electrochemical testing methods. It was revealed that the secondary phase of Al₂O₃ particles mainly distributed along grain boundaries of Cr₂AlC matrix. The potentiodynamic polarization measurements showed that the corrosion current densities of these Cr₂AlC composites were lower than that of the pure Cr₂AlC. The Aluminum in Cr₂AlC was prone to be attacked more easily. When immersed at open circuit potential (OCP), Al readily slipped out from Cr₂AlC matrix into NaCl solution in the form of dissoluble species. But in the case of polarization, regardless of potentiostatic polarization or potentiodynamic polarization, more de-intercalated Al, reacted with the electrolyte to form corrosion products of Al₂O₃ and/or AlOOH and deposited on the sample surface. For Cr₂AlC/α-Al₂O₃ composites, the presence of Al₂O₃ weakened the corrosion along grain boundaries by partly blocking the permeation of electrolyte and inhibiting the anodic dissolution process.     

Corrosion Behaviour of Niobium in Sodium Hydroxide Solutions

The electrochemical behaviour of niobium was investigated in sodium hydroxide solutions at different temperatures, using open-circuit potential (OCP) measurements, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). OCP and polarization measurements show that Nb is spontaneously active in 10, 15 and 30 wt % NaOH at 25, 50 and 75 °C. The anodic polarization curves in all cases show a dissolution/passivation peak followed by a current plateau, corresponding to Nb₂O₅ formation. The spontaneous active corrosion of Nb leads to the formation of soluble niobates that precipitate to sodium niobates. The evaluation of the corrosion current densities obtained from Tafel extrapolation of polarization curves and the polarization resistance values determined from EIS measurements indicates that the corrosion rates of niobium increase with increasing NaOH concentration and temperature.     

Ruthenium dioxide: a new electrode material. I. Behaviour in acid solutions of inert electrolytes

The electrochemical behaviour of RuO₂ film electrodes, prepared by the thermal decomposition of Ru Cl₃ on metallic supports has been investigated in solutions of inert electrolytes. Steady-state pot entiostatici/E curves, cyclic voltammetry and charging curves are presented. The procedure for the preparation of electrodes is described. RuO₂ film electrodes exhibit oxygen overvoltages much lower than, and hydrogen overvoltages almost equal to, those on Pt electrodes. Results of measurements in the range of potential between oxygen and hydrogen evolution suggest that modifications arise which, while occurring within the whole film and not only at the surface, involve only a small fraction of the metal atoms. An explanation of this behaviour is advanced in terms of non-stoichiometry of the oxide layer.     

Preparation and electrochemical performance of uniform RuO2/Ti and RuO2‐IrO2/Ti electrode for electrolysis of NaCl solution

The electrochemical preparation of NaClO has been widely used for the production of industrial disinfectant. To reduce the cost of electrode preparation using the brushing method, this paper introduces a method for the electrodeposition for RuO₂/Ti and RuO₂‐IrO₂/Ti preparation and NaCl solution electrolysis. The deposition of Ir improves the uniformity and stability of the RuO₂/Ti electrode. The optimum preparation conditions and additive concentrations were investigated in detail through the orthogonal experiment. By adjusting the electroplating time, temperature and voltage, the electrode with a high content of available chlorine was synthesized successfully. The physicochemical properties of the as‐prepared RuO₂/Ti and RuO₂‐IrO₂/Ti were determined by XRD, SEM‐EDS, and XPS, and the electrochemical performance and lifetime of the RuO₂/Ti and RuO₂‐IrO₂/Ti was verified via an electrochemical workstation. Uniform and stable RuO₂/TiO₂ and RuO₂‐IrO₂/TiO₂ were synthesized successfully for the electrolysis of the NaCl solution.     

The corrosion behavior of sputter-deposited aluminum-tungsten alloys

Thin films on aluminum-tungsten alloys were prepared by co-deposition of pure aluminum and pure tungsten, each sputtered by an independently controlled magnetron source, on glass and sapphire substrates. Completely amorphous films were obtained in the Al₈₀W₂₀-Al₆₇W₃₃ composition range. Passivity and corrosion behavior of amorphous Al-W alloys were investigated in 1 M deaerated hydrochloric acid solution using polarization and impedance spectroscopy measurements and have been correlated with the properties of pure alloy components. Tungsten and sputter-deposited Al-W thin films are inherently passive materials while aluminum undergoes pitting corrosion in hydrochloric acid solution. The passive film formed at the OCP on each alloy possesses excellent electric and dielectric properties comparable to those of the isolating film on tungsten. The absolute impedance increases with increasing tungsten content in the alloy. According to electrochemical polarization measurements, alloying Al with W in solid solution significantly enhances the material's resistance to pitting corrosion by shifting the breakdown potential above 2000 mV (Al₆₇W₃₃) and lowering the corrosion rate at the OCP by more than two orders of magnitude. The most likely mechanism explaining the passivity of amorphous Al-W alloys, the Solute Vacancy Interaction Model (SVIM), involves the formation of complexes between highly oxidized solute atoms (W⁺⁶) and mobile cation vacancies, which restrict the transport of Cl⁻ through the oxide film and inhibit its breakdown in hydrochloric acid solution. The role that film stress relaxation effects and microscopic defects in amorphous Al-W films, of the some composition, and deposited on various substrates play in their corrosion resistance is discussed.     

Effects of Cr2N on the pitting corrosion of high nitrogen stainless steels

Effects of nitrogen (N) content on the precipitation behavior of Cr₂N with its relevant influences on the resistance to localized corrosion of high nitrogen stainless steels (HNSs) were examined using an electrochemical microcell. HNS of Fe-18Cr-20Mn-3Mo-1.07N was highly resistant to pitting corrosion. With aging the alloy at 900 °C, Cr₂N precipitated initially along grain boundaries, then within grain, and eventually formed a lamellar structure, accompanied with a drastic decrease in the resistance to pitting corrosion. It was found from the electrochemical microcell tests that the lamellar Cr₂N was the most susceptible site for pitting corrosion when compared with any other heterogeneity such as a (Mn, Cr)-oxide or a Cr₂N precipitated along the grain boundaries.     

Covalent attachment of pyridine-type molecules to glassy carbon surfaces by electrochemical reduction of in situ generated diazonium salts. Formation of ruthenium complexes on ligand-modified surfaces

In this study, pyridine, quinoline and phenanthroline molecules were covalently bonded to glassy carbon (GC) electrode surfaces for the first time using the diazonium modification method. Then, the complexation ability of the modified films with ruthenium metal cations was investigated. The derivatization of GC surfaces with heteroaromatic molecules was achieved by electrochemical reduction of the corresponding in situ generated diazonium salts. X-ray photoelectron spectroscopy (XPS) was used to confirm the attachment of heteroaromatic molecules to the GC surfaces and to determine the surface concentration of the films. The barrier properties of the modified GC electrodes were studied in the presence of redox probes such as Fe(CN)₆³⁻ and Ru(NH₃)₆³⁺ by cyclic voltammetry. Additionally, the presence of the resulting organometallic films on the surfaces was verified by XPS after the chemical transformation of the characterized ligand films to the ruthenium complex films. The electrochemical behavior of these films in acetonitrile solution was investigated using voltammetric methods, and the surface coverage of the organometallic films was determined from the reversible metal-based Ru(II)/Ru(III) oxidation waves.     

Morphological and electrochemical investigation of RuO<Subscript>2</Subscript>–Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> oxide films prepared by the Pechini–Adams method

Preparation methods can profoundly affect the structural and electrochemical properties of electrocatalytic coatings. In this investigation, RuO₂–Ta₂O₅ thin films containing between 10 and 90 at.% Ru were prepared by the Pechini–Adams method. These coatings were electrochemically and physically characterized by cyclic voltammetry, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The composition and morphology of the oxide were investigated before and after accelerated life tests (ALT) by EDX and SEM. SEM results indicate typical mud-flat-cracking morphology for the majority of the films. High resolution SEMs reveal that pure oxide phases exhibit nanoporosity while binary compositions display a very compact structure. EDX analyses reveal considerable amounts of Ru in the coating even after total deactivation. XRD indicated a rutile-type structure for RuO₂ and orthorhombic structure for Ta₂O₅. XPS data demonstrate that the binding energy of Ta is affected by Ru addition in the thin films, but the binding energy of Ru is not likewise influenced by Ta. The stability of the electrodes was evaluated by ALT performed at 750 mA cm⁻² in 80 °C 0.5 mol dm⁻³ H₂SO₄. The performance of electrodes prepared by the Pechini–Adams method is 100% better than that of electrodes prepared by standard thermal decomposition.     

Reactivity at the film/solution interface of ex situ prepared bismuth film electrodes: A scanning electrochemical microscopy (SECM) and atomic force microscopy (AFM) investigation

Bismuth film electrodes (BiFEs) prepared ex situ with and without complexing bromide ions in the modification solution were investigated using scanning electrochemical microscopy (SECM) and atomic force microscopy (AFM). A feedback mode of the SECM was employed to examine the conductivity and reactivity of a series of thin bismuth films deposited onto disk glassy carbon substrate electrodes (GCEs) of 3 mm in diameter. A platinum micro-electrode (? = 25 μm) was used as the SECM tip, and current against tip/substrate distance was recorded in solutions containing either Ru(NH₃)₆³⁺ or Fe(CN)₆⁴⁻ species as redox mediators. With both redox mediators positive feedback approach curves were recorded, which indicated that the bismuth film deposition protocol associated with the addition of bromide ions in the modification solution did not compromise the conductivity of the bismuth film in comparison with that prepared without bromide. However, at the former Bi film a slight kinetic hindering was observed in recycling Ru(NH₃)₆³⁺, suggesting a different surface potential. On the other hand, the approach curves recorded by using Fe(CN)₆⁴⁻ showed that both types of the aforementioned bismuth films exhibited local reactivity with the oxidised form of the redox mediator, and that bismuth film obtained with bromide ions exhibited slightly lower reactivity. The use of SECM in the scanning operation mode allowed us to ascertain that the bismuth deposits were uniformly distributed across the whole surface of the glassy carbon substrate electrode. Comparative AFM measurements corroborated the above findings and additionally revealed a denser growth of smaller bismuth crystals over the surface of the substrate electrode in the presence of bromide ions, while the crystals were bigger but sparser in the absence of bromide ions in the modification solution.     

Electrochemical and spectroelectrochemical monitoring of supercapacitance and electrochromic properties of hydrous ruthenium oxide embedded poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) composite

A new composite film was prepared by depositing hydrous ruthenium oxide (RuO₂) particles into a polymer matrix comprising of poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(styrene sulfonic acid) (PSS). The composite, PEDOT-PSS-RuO₂, showed an enhanced capacitance and optical properties due to the presence of RuO₂ particles in the composite. Specific capacitance of the PEDOT-PSS-RuO₂ composite was found to be 1409 F/g. After anodic polarization, the PEDOT-PSS-RuO₂ composite film exhibited enhanced visible-light coloration in comparison with PEDOT/PSS and simple RuO₂ films. Differential voltabsorptometric curves (dA/dt versus potential (derivative cyclic voltabsorptogram, DCVA)) were deduced for few selected wavelengths to characterize the optical properties. The changes in the electrochromic characteristics (in the visible region) of the composite is attributed mainly to transition of Ru(III) to Ru(IV). SEM images revealed the presence of smaller sized particles of hydrous ruthenium oxide in the composite film. The existence of smaller size RuO₂ particles having more active surface area is the reason for the enhanced capacitance and optical properties.     

Pt–Ru nanoparticles supported on functionalized carbon as electrocatalysts for the methanol oxidation

Platinum–ruthenium alloy electrocatalysts, for methanol oxidation reaction, were prepared on carbons thermally treated in helium atmosphere or chemically functionalized in H₂O₂, or in HNO₃ + H₂SO₄ or in HNO₃ solutions. The functionalized carbon that is produced using acid solutions contains more surface oxygenated functional groups than carbon treated with H₂O₂ solution or HeTT. The XRD/HR-TEM analysis have showed the existence of a higher alloying degree for Pt–Ru electrocatalysts supported on functionalized carbon, which present superior electrocatalytic performance, assessed by cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy, as compared to electrocatalysts on unfunctionalized carbon. It also was found that Pt–Ru alloy electrocatalysts on functionalized carbon improve the reaction rate compared to Pt–Ru on carbons treated with H₂O₂ solution and thermally. A mechanism is discussed, where oxygenated groups generated from acid functionalization of carbon and adsorbed on Pt–Ru electrocatalysts are considered to enhance the electrocatalytic activity of the methanol oxidation reaction.     

Effect of Ru and LaNiO3 barrier layers on lead zirconate titanate films grown on nickel-based metal foils by sol–gel process

Lead zirconate titanate [Pb(Zr_0.52, Ti_0.48)O₃ (PZT)] films were grown by sol–gel process on nickel and hastelloy foils. PZT perovskite phase was obtained at 650 °C annealing condition and surface topography showed uniform and dense microstructure. The characterization on dielectric properties indicates that diffusion of foil elements into the PZT and the formation of low capacitance interfacial layer occur during process. In order to reduce the diffusion effect of foil element and/or interfacial layer, barrier layers such as Ru(RuO₂) and LaNiO₃ layers were utilized on foil substrates. The increase of grain size was observed in PZT films grown on barrier layers. Dielectric properties are greatly improved without degrading ultimate dielectric breakdown strength.     

High activity PtRu/C catalysts synthesized by a modified impregnation method for methanol electro-oxidation

A modified impregnation method was used to prepare highly dispersive carbon-supported PtRu catalyst (PtRu/C). Two modifications to the conventional impregnation method were performed: one was to precipitate the precursors ((NH₄)₂PtCl₆ and Ru(OH)₃) on the carbon support before metal reduction; the other was to add a buffer into the synthetic solution to stabilize the pH. The prepared catalyst showed a much higher activity for methanol electro-oxidation than a catalyst prepared by the conventional impregnation method, even higher than that of current commercially available, state-of-the-art catalysts. The morphology of the prepared catalyst was characterized using TEM and XRD measurements to determine particle sizes, alloying degree, and lattice parameters. Electrochemical methods were also used to ascertain the electrochemical active surface area and the specific activity of the catalyst. Based on XPS measurements, the high activity of this catalyst was found to originate from both metallic Ru (Ru⁰) and hydrous ruthenium oxides (RuO_xH_y) species on the catalyst surface. However, RuO_xH_y was found to be more active than metallic Ru. In addition, the anhydrous ruthenium oxide (RuO₂) species on the catalyst surface was found to be less active.     

Effect of mixing glass frits on electrical property and microstructure of sintered Cu conductive thick film

The resistivity of the sintered Cu thick film decreases with the weight percentage of the SiO₂–ZnO–B₂O₃ additive in the mixing glass frits up to 50 wt%. As the weight percentage of the SiO₂–ZnO–B₂O₃ additive in the mixing glass frits is over 50 wt%, the resistivity of the sintered Cu thick films is quite similar. The lowest resistivity (6.62 × 10⁻⁶ Ω-cm) of the sintered Cu thick films occurs at 75 wt% of the SiO₂–ZnO–B₂O₃ additive. Also, we observe the extensive glass phase framing around the large Cu grains in the Cu thick films sintered with low SiO₂–ZnO–B₂O₃ additives (less than 50 wt%) narrows the cross-section area of the electrical path. On the contrary, the round-shaped glass phase solidified among the small Cu grains allows a larger cross-section of the electrical path (a possible lower resistivity) for the Cu thick films sintered with higher SiO₂–ZnO–B₂O₃ additives (larger than 50 wt%). The above results imply that the resistivity of the sintered Cu thick film correlates well with the microstructure (Cu grain size and the glass/Cu composite structure) of the sintered Cu thick films. Twin grain boundaries can clearly be observed in the sintered Cu thick films, especially for the Cu thick film sintered with the higher SiO₂–ZnO–B₂O₃ additives. Owing to small Cu grains size and high density of Cu grain boundary, the probability of the grain boundaries with a high grain-boundary energy in the Cu thick film sintered with high SiO₂–ZnO–B₂O₃ additive would be much larger, comparing to that in the Cu thick film sintered with low SiO₂–ZnO–B₂O₃ additive. Thus, more annealing twin boundaries formed in the Cu thick film sintered with high SiO₂–ZnO–B₂O₃ additive. Hence, the formation of the twin boundary in the sintered Cu thick film helps reducing the resistivity of the sintered Cu films.     

A kinetical model for the electrochemical grooving of grain boundaries

In the case of FeNiCr alloys (without precipitation), we propose an electrochemical method which allows us to obtain a reproducible selective corrosion of grain boundaries (H₂SO₄-2N-25°C in the transpassive domain). We establish a model of dissolution to explain the morphology of etched grooves. From this model we deduce a parameter α₀ which characterizes the intergranular corrosion susceptibility of a given alloy.Electrochemical kinetic allows us to calculate the ratio of the density of active sites at the emergence of the grain boundary and on the surface of the grain. This electrochemical method permits us to study the effects of the segregation phenomena, of composition alloy and of grain boundary structure on intergranular corrosion.     

Electrochemical corrosion of solid and liquid phase sintered silicon carbide in acidic and alkaline environments

Solid and liquid phase sintered silicon carbide (SiC) ceramics are used in aggressive environments, e.g. as seals and linings in chemical plant equipments. There exist data concerning corrosion of solid phase sintered SiC (SSiC), but there are only few data concerning their electrochemical corrosion behaviour. The corrosion of liquid phase sintered SiC ceramics (LPS SiC) containing yttria aluminium oxide grain boundary phases has been investigated by standard methods that have shown the decisive influence of the oxide grain boundary on the corrosion stability of these materials. But no electrochemical investigations are known. In this study therefore, potentiodynamic polarisation measurements have been used to determine the corrosion mechanisms of SSiC and LPS SiC ceramics at room temperature in acidic and alkaline environments. The investigation has shown a pronounced electrochemical corrosion in acids and alkaline solutions for both types of materials. In HCl and HNO₃ pseudo-passivity features due to the formation of a thin layer of SiO₂ on the surface were observed, whereas in NaOH soluble silicate ions were observed resulting in more pronounced corrosion. Microstructural observations of initial and corroded samples revealed that the residual carbon found in the microstructure of SSiC did not dissolve preferentially. The corrosion current densities of the LPS SiC materials were caused by the dissolution of SiC and not by the corrosion of the oxide grain boundary phase. The corrosion current densities of the LPS SiC materials investigated were lower than those of the SSiC materials.     

The oxygen evolution reaction on platinum,iridium, ruthenium and their alloys at 80°C in acid solutions

Kinetic parametes were determined for the oxygen evolution reaction on 50–50 atom percent alloys of RuIr, RuPt, and IrPt and compared with results obtained using ruthenium, iridium, platinum, and RuO₂/TiO₂ electrodes. The potentiostatic studies were made on oxide covered electrodes at 80°C in both 1.0 M H₂SO₄ and 1.0 M CF₃SO₃H. Cyclic voltammetric studies showed that while these noble metals and alloys are about equally effective as electrocatalysts for the hydrogen evolution reaction, striking differences in activity are found for the oxygen evolution reaction. The order of electrocatalytic activity towards oxygen evolution in H₂SO₄ is Ru > RuIr alloy ～ RuO₂/TiO₂ ～ Ir > IrPt alloy > RuPt alloy > Pt. The type of acid used had very little effect on the kinetic parameters. The lower electrocatalytic activities when platinum is present is probably due to the formation of a platinum oxide film. The dual barrier model is used to interpret the results for the electrodes containing platinum. The best electrocatalysts for oxygen evolution in acid solutions consist of noble metals which form oxide films (RuO₂, IrO₂) possessing metallic characteristics.     

The corrosion protection of mild steel by single layered polypyrrole and multilayered polypyrrole/poly(5-amino-1-naphthol) coatings

Electrochemical synthesis of polypyrrole (PPy) and top coat of poly(5-amino-1-naphthol) (PANAP) on PPy films from oxalic acid solution was achieved on mild steel (MS) by cyclic voltammetry technique. The morphology and the structure of the films were investigated by scanning electron microscopy (SEM). The corrosion performance of this multilayer coating and single PPy coating were investigated in 3.5% NaCl solution by using open circuit potential (E_ocp)–time curves, polarization curves and electrochemical impedance spectroscopy (EIS). It was found that the multilayer PPy/PANAP coating could provide much better protection than single PPy coating for corrosion of MS. It was observed that corrosion performance of coatings was increasing with immersion period. This was explained by auto-undoping properties of PPy coatings during immersion in corrosive solution. The improved corrosion performance in the presence of PANAP top coat on PPy was explained by increase in barrier effect of bilayer films.     

Effects of minor additions of ruthenium on the passivation of duplex stainless-steel corrosion in concentrated hydrochloric acid solutions

The effects of minor additions of ruthenium (0.14%, 0.22%, and 0.28%) on the passivation of duplex stainless-steel (DSS, Fe–22%Cr–9%Ni–3%Mo) corrosion in 2 M HCl solutions have been studied using open-circuit potential (OCP), potentiodynamic cyclic polarization, potentiostatic current–time, electrochemical impedance spectroscopy (EIS), and weight loss measurements. OCP measurements showed an increased shift in the corrosion potential to more positive values with increasing Ru content. Polarization and EIS experiments indicated that the presence of Ru and the increase of its content decrease the corrosion rate, critical and passive current density, and polarization resistance. Moreover, it shifts the corrosion and pitting potentials to more positive values. Current–time measurements at −100, −50, and 50 mV versus Ag/AgCl also confirmed that the severity of pitting corrosion decreases with an increasing Ru content. Weight-loss time data showed good agreement with the electrochemical measurements.     

Corrosion inhibition of stainless steel by polyaniline,poly(2-chloroaniline), and poly(aniline-co-2-chloroaniline) in HCl

Polyaniline (PANi), poly(2-chloroaniline) (PClANi), and poly(aniline-co-2-chloroaniline) (co-PClANi) films were synthesized by electrochemical deposition on 304-stainless steel (SS) from an acetonitrile solution. The structural properties of these polymer films were characterized by spectroscopic (FTIR and UV–vis) and electrochemical (cyclic voltammetry) methods. Open circuit potential–time (E_ocp–time) curves, potentiodynamic polarization, and electrochemical impedance (EIS) measurements showed that these films have significant protective performance against corrosion of SS in 0.5 M HCl solution. It was found that co-PClANi film has acted as a passivator as well as barrier for cathodic reduction reaction in a similar manner as PANi film. However, PClANi film has behaved only as barrier for corrosion protection of SS in 0.5 M HCl.