The influence of nanocrystalline state of iron on the corrosion inhibitor behavior in aqueous solution

Effect of grain size reduction on the electrochemical and corrosion behavior of iron of different grain sizes (32–320 nm) produced by direct and pulsed current electrodeposition was characterized using Tafel polarization curves and electrochemical impedance spectroscopy (EIS). The grain size of deposits was determined by X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM). The most intensive first-order peak (110) of the XRD patterns was taken for detailed analysis using a Gaussian fitting curve. The electrochemical tests were carried out in electrolyte 30 mg L⁻¹ NaCl + 70 mg L⁻¹ Na₂SO₄ + 250 mg L⁻¹ NaNO₂ aqueous solution. It was found that the corrosion potential and corrosion current density significantly changed as the microstructure morphology was changed. Results obtained from electrochemical tests suggested that the inhibition effect and corrosion protection of sodium nitrite inhibitor in near-neutral aqueous solutions increased as the grain size decreased from submicrocrystalline to nanocrystalline. This was attributed to the excess free energy, and concomitantly the increased number of the active sites caused by higher grain boundary and triple junction content in the nanocrystalline surface, which provides sites for electrochemical activity, and effect of sodium nitrite, was more pronounced.     

Role of a clay sediment deposit on the passivity of carbon steel in 0.1 mol dm NaHCO3 solutions

The role of clays in the corrosion processes of carbon steel was investigated. Four different minerals, silica, kaolinite, chlorite and montmorillonite, were considered. They were deposited by sedimentation on carbon steel electrodes. The electrochemical behaviour of steel electrodes covered with mineral deposits was studied in 0.1 mol L⁻¹ NaHCO₃ solutions by cyclic voltammetry (4 cycles between −0.8 V/SCE and −0.1 V/SCE) and compared to that of a bare electrode. Potentiostatic experiments were performed at −0.62 V/SCE, close to the corrosion potential, and the interfacial processes were investigated by electrochemical impedance spectroscopy. Analysis of the corrosion products accumulated at the inner side of the deposited mineral layer was performed by μ-Raman spectroscopy. As it could be expected, the deposits hindered the transport of dissolved oxygen and Fe(II) species, inducing changes in the interfacial solution and modification of the composition of the rust layer. Moreover, specific interactions between minerals and dissolved Fe species also influenced the corrosion processes.     

Enhancement of Corrosion Resistance Properties of Electrodeposited Ni/nano-TiC Composite Layers

This paper presents novel results on the effects of the dispersion of titanium carbide nanoparticles (50 nm mean diameter) into a nickel-plating electrolyte on the corrosion behavior of the nanocomposite layers obtained. The Ni/nano-TiC layers are compared with pure nickel layers obtained at the same electrodeposition parameters with 60 mA·cm⁻² current density and 10 min deposition time. The comparative corrosion performances are investigated using a three-electrode electrochemical cell in a solution (mixed boric acid with lithium hydroxide), which simulates the primary water circuit of pressurized water reactors (PWRs). Open circuit potential measurement and electrochemical impedance spectroscopy were employed as the electrochemical methods, using an electrochemical workstation connected to an electrochemical cell, as well as a PC with software to drive the experimental work. The results clearly revealed enhanced corrosion properties for the Ni/nano-TiC hybrid layers as compared to the pure Ni layers. The significantly improved corrosion behavior can be attributed to the TiC nanoparticles embedded into the Ni matrix, which have the effect of insulating centers at the composite layer/corrosive solution interface.     

Deposition and characterization of nickel–niobium composite electrocoatings

Ni–Nb composite electrocoatings were obtained on carbon steel from Watts bath, containing suspended 20 μm size niobium powders. The effect of cathodic current density, electrolyte stirring rate and concentration of Nb particles in the bath on the deposit morphology and texture, volume fraction of co-deposited Nb particles and microhardness was investigated. The Ni–Nb composite layers presented a rough morphology with randomly oriented Ni grains, whereas pure Ni coatings obtained under the same experimental conditions were smooth and showed highly preferred orientation in the [110] or [100] direction. Stirring rate of the electrolyte and concentration of Nb particles in the bath are the main parameters affecting the incorporation of Nb particles. The Nb incorporated volume fraction was 11–14%, 17–19%, 27–32% and 34–37% for the 20 g L⁻¹ Nb/550 rpm, 20 g L⁻¹ Nb/400 rpm, 40 g L⁻¹ Nb/400 rpm and 40 g L⁻¹ Nb/550 rpm conditions, respectively. The microhardness of the Ni–Nb composite coatings obtained at 20 and 40 mA cm⁻² was higher than that of pure Ni layers, due to grain refining. Incorporation of Nb particles in Ni coatings improved the corrosion resistance of the deposits in NaCl and H₂SO₄ solutions.     

Electrochemical corrosion behaviors of Ti3SiC2/Cu composites in a 3.5% NaCl solution

The electrochemical corrosion behaviors of Ti₃SiC₂/Cu composite and polycrystalline Ti₃SiC₂ in a 3.5% NaCl medium were investigated by dynamic potential polarization, potentiostat polarization, and electrochemical impedance spectroscopy. The polycrystalline Ti₃SiC₂ was tested on the identical condition as a control. The characterizations of XRD, X-ray photoelectron spectroscopy, scanning electron microscope, and energy-dispersive spectrometer were used to study the relevant passivation behavior and corrosive mechanism. The self-corrosion current density of Ti₃SiC₂/Cu (6.46 × 10⁻⁶ A/cm²) was slightly higher than that of Ti₃SiC₂ (1.64 × 10⁻⁷ A/cm²). Under open circuit potential, the corrosion resistance of Ti₃SiC₂/Cu was better than that of Ti₃SiC₂. Ti₃SiC₂/Cu exhibited a typical passivation feature with a narrow passivation interval and a breakdown phenomenon. The better corrosion resistance of Ti₃SiC₂ was due to the more stable Si layer of the former. In comparison, for Ti₃SiC₂/Cu composites, Cu reacted with the reactive Si layers in Ti₃SiC₂ to form Cu–Si compounds and TiC, destroying the weak interaction between Si layers and Ti–C layers. In the other hand, the as-formed Cu–Si compounds and TiC dissolved during the corrosion of Ti₃SiC₂/Cu in the 3.5% NaCl medium, causing to the destruction of the passivation film on its surface.     

Electrochemical study of corrosion behavior of graphene coatings on copper and aluminum in a chloride solution

Electrochemical characteristics and corrosion behavior of graphene coatings on Cu and Al in a 0.1 M NaCl solution were investigated. The graphene coatings were deposited on a Cu surface by chemical vapor deposition. Multiple graphene layers were then mechanically transferred from the growth substrate, Cu, onto Al surface by a transfer technique. The corrosion stability of graphene coatings was determined by electrochemical impedance spectroscopy and open circuit potential, while the corrosion rate was evaluated using potentiodynamic sweep measurements. Surface morphologies of the graphene coatings were analyzed by scanning electron microscopy and energy dispersive spectroscopy. Obtained results indicate that Cu coated with graphene grown using chemical vapor deposition shows corrosion-inhibiting properties in 0.1 M NaCl. On the other hand, Al coated with a multilayer graphene film mechanically transferred from the Cu surface exhibits electrochemical characteristics similar to an Al oxide on bare Al. Better protective properties of graphene coating on Cu compared to the graphene coating on Al were observed, probably due to the breakage of Al oxide film, causing the corrosion of Al to proceed rapidly in the presence of chloride electrolyte.     

Erosive and corrosive wear performance and characterization studies of plasma-sprayed WC/Cr3C2 coating on SS316

Plasma spray coating with ceramic carbide is a promising approach for improving the surface quality of the materials. In this work, the effectiveness of tungsten carbide (WC), chromium carbide (Cr₃C₂), and the composite coating of the two powders in the weight ratio of 50:50 were investigated. In the erosion test, aluminum oxide (Al₂O₃) particles were combined with a high-speed air-jet and impinged at 90° on the top surface of the material. Electrochemical polarization and electrochemical impedance spectroscopy studies were conducted with a 3.5 wt.% of sodium chloride (NaCl) solution as the electrolyte. Using a scanning electron microscope, the surface morphology of powders and coatings, as well as the mechanisms of erosion and corrosion, were studied. Energy-dispersive X-ray analysis and X-ray diffractometry were used to reveal the composition and elemental distribution of the feedstock powders and coatings. Because of the presence of hard phases, the composite coating shows the highest average microhardness of 1350.2 HV. The composite coating exhibits improved erosive wear resistance with an increase in erodent exposure time. The Cr₃C₂ coating has a reduced corrosion current density of 1.404 × 10⁻⁵ mA/cm² and a higher charge transfer resistance of 2086.75 Ω cm² due to passivation.     

Microstructure and corrosion properties of Ni-TiN nanocoatings prepared by jet pulse electrodeposition

Ni–TiN nanocoatings were successfully prefabricated by jet pulse electrodeposition. The effect of jet rate on cross-sectional composition, microstructure, microhardness, and corrosion properties of nanocoatings was examined by X-ray photoelectron spectroscopy, high-resolution transmission electron microscope, atomic force microscopy, microhardness tester and electrochemical workstation. Results illustrated that Ni–TiN nanocoatings deposited at jet rate of 3 m/s exhibited high concentration of Ni and Ti with average concentrations of Ni and Ti of 54.5 at% and 19.8 at%, respectively. Average diameters of Ni grains and TiN nanoparticles in Ni–TiN nanocoatings prepared at 3 m/s were 47.8 nm and 30.5 nm, respectively. Nanocoatings deposited at 1 m/s, 3 m/s and 5 m/s showed surface root-mean-square roughness value of 95.431, 30.091 and 58.454 nm, respectively, and presented maximum microhardness of 789.5, 876.2, and 849.9 HV, respectively. Ni–TiN nanocoating obtained at 3 m/s demonstrated minimum I_corr and E_corr values of 1.02 × 10⁻³ mA/cm² and − 0.551 V, respectively, signifying to offer the best corrosion resistance.     

Improving the corrosion resistance of a-C:H film by a top a-C:H:Si:O layer

During the deposition of a-C:H film, defects (pinholes or discontinuities) caused by excessive stress will inevitably appear, which will reduce the corrosion resistance of the a-C:H film. In this study, top a-C:H:Si:O layers (thickness of approximately 0.3 μm) on the surface of a-C:H films were deposited on a large scale by PACVD technology using acetylene (C₂H₂) and/or hexamethyldisiloxane (HMDSO) as reactants, to improve the corrosion resistance of a-C:H films while ensuring the appropriate overall hardness of the films. The corrosion behaviors of the films were studied by electrochemical impedance spectroscopy (EIS) and Tafel polarization. We found that the a-C:H/a-C:H:Si:O films possess a lower electrolyte penetration rate due to their stronger capacitance characteristics. In addition, the corrosion current density of the a-C:H/a-C:H:Si:O films (10^?10 A cm^?2) were reduced by 2 orders of magnitude compared to the a-C:H film (10^?8 A cm^?2), and by 3 orders of magnitude compared to 316 stainless steel (10^?7 A cm^?2). The impedance results obtained by EIS were simulated using appropriate equivalent circuits, and the corresponding electrical parameters were used to further verify the electrochemical protection behavior of the top a-C:H:Si:O layer.     

The influence of pulse plating parameters on microstructure and properties of Ni-W-Si3N4 nanocomposite coatings

Nanosized silicon nitride (Si₃N₄) particles reinforced Nickel-tungsten composite coatings were deposited on the surface of C45 steel sheet by pulse electrodeposition. The effect of duty cycle, frequency, current pattern and presence of Si₃N₄ nanoparticles on microstructure, phases and corrosion resistance and mechanical properties of the coatings were investigated. The Si₃N₄ phase was incorporated into Ni-W alloy matrix uniformly and the inclusion content of in the coating was analyzed by energy dispersive x-ray spectrometer (EDS). The structure, microhardness and surface roughness of the coatings was analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), Vickers micro-indenter and atomic force microscopy (AFM). The corrosion protection of steel by the coatings was evaluated by weight loss and electrochemical impedance spectroscopy (EIS). Corrosion rates of the coatings were determined using the Tafel polarization test. The results indicated that the duty cycle of 60%, pulse frequency of 1000 Hz, average current density of 5 A/dm⁻², and Si₃N₄ nanoparticles concentration of 30 g/L were the optimal plating conditions. The amount of Si₃N₄ particles incorporated into the coating that were produced under the optimum plating conditions was 2.1 wt%, and the microhardness was 1031 Hv as well as the crystallite size of this coating was 27 nm.     

Corrosion behavior of ferritic stainless steel alloyed with different amounts of niobium in hydrochloric acid solution

The corrosion behavior of stainless steel alloys containing corrosion-resistant elements was investigated. Ferritic stainless steel (FSSs) electrodes were synthesized by applying a scan rate of 1 mV s⁻¹. Stainless steels were used unalloyed and alloyed with about 0.5, 1, and 3 wt% elemental Nb. The samples were obtained from casting and forging. The samples were classified into three groups. In the first group, samples were unhomogenized and remained in production condition. In the second and third groups, samples were exposed to homogenization at 1,100 °C for 30 min or 180 min, respectively, and then quenched. The corrosion performance of the FSSs was investigated in 0.3 M HCl acid solution using electrochemical impedance spectroscopy (EIS). Corrosion resistance was calculated using the Stearn–Geary equation. SEM investigations of samples immersed in 0.3 M HCl acid solution for 60 and 360 min were performed. SEM micrographs showed generalized pitting. Consequently, it was determined that niobium has a beneficial effect on the corrosion resistance of FSS since niobium reacts with carbon to form stable carbides.     

Dodigen 213-N as corrosion inhibitor for ASTM 1010 mild steel in 10% HCL

This article describes a study of the behavior of a mixture of amines and amides, commercially known as Dodigen 213-N (D-213 N), as a corrosion inhibitor for ASTM 1010 mild steel in 10% w/w HCl solution. The concentration range used was 1 × 10⁻⁵ M to 8 × 10⁻⁴ M. The weight loss and electrochemical techniques used were corrosion potential measurement, anodic and cathodic polarization curves, and electrochemical impedance spectroscopy (EIS). The solution temperature was 50 ± 1 °C and it was naturally aerated. The corrosion potential values shifted to slightly more positive values, thus indicating mixed inhibitor behavior. The anodic and cathodic polarization curves showed that D-213 N is an effective corrosion inhibitor, since both the anodic and the cathodic reactions were polarized in comparison with those obtained without inhibitor. For all concentrations the cathodic polarization curves were more polarized than the anodic ones. The inhibition efficiency was in the range 75–98%, calculated from values of weight loss and corrosion current density, i _corr, obtained by extrapolation of Tafel cathodic linear region.     

Electrochemical investigations on the corrosion behavior and corrosion natural inhibition of API-X100 pipeline steel in acetic acid and chloride-containing CO<Subscript>2</Subscript>-saturated media

The purpose of this experimental work was to investigate selected electrochemical aspects of the corrosion behavior of API-X100 in CO₂-saturated, multivariable-controlled corrosion media. Utilizing potentiodynamic polarization and electrochemical impedance spectroscopy (EIS), the corrosion rates, anodic dissolution, cathodic regimes, and free interfacial interactions were discussed. The tests were performed with respect to the environmental factors of 10, 20, 30, 40, 50, and 60 g L⁻¹ chloride and of 10, 20, 30, 40, 50, and 60 mL L⁻¹ acetic acid at 20 and 90 °C in the absence and presence of 10 vol% crude oil. The corrosion rates exhibited a peak value with respect to the chloride content while they increased continuously with the acetic acid content irrespectively from temperature. The corrosion behavior was nearly independent from chloride in the presence of acetic acid and oil demonstrated an effective inhibition in all conditions. EIS results showed an agreement with the polarization findings and indicated adsorption-controlled mechanisms.     

Electrochemical behavior of current collectors for lithium batteries in non-aqueous alkyl carbonate solution and surface analysis by ToF-SIMS

Several metals (Cu, Fe, Al, Ti, and Cr) as current collector for lithium-ion battery were investigated to understand their electrochemical behavior and passivation process in a non-aqueous alkyl carbonate solution containing LiPF₆ salt. From cyclic voltammetric study, it was found that Cu and Fe metals were dissolved into the electrolyte below 4 V vs. Li/Li⁺. Alternatively, Al and Ti were stable up to 5 V vs. Li/Li⁺. Their scratched surfaces at 5 V vs. Li/Li⁺ were polarized in a transient mode and it was found that the surfaces were passivated during the polarization test. Formed passive film was composed of two hybrid layers: outer layer by metal (Al and Ti) fluoride and inner by metal oxide, as confirmed by time-of-flight secondary ion mass spectroscopy. Presence of HF in the electrolyte was indispensible to form the metal fluoride layer on the oxide layer. The outer fluoride layer would protect the inner oxide layer and metal substrate from HF attack, bringing about satisfactory corrosion resistance under lithium-ion battery environment.     

Zn–Ni/nano-TiO2 composite electrodeposits: surface modifications and protective properties

Zn–Ni composite coatings were obtained by electrochemical co-deposition of TiO₂ nano-particles (mean diameter 21 nm). Zn–Ni alloy coating was also produced under the same experimental conditions for comparison. The surface morphology, crystallographic structure, and the grain size of the deposits were investigated, along with the percentage of the embedded nano-particles in Zn–Ni matrix, as a function of concentration of TiO₂ nano-particles in the bath. As the titania incorporation percentage is increased, a grain refinement in the nanometer region was revealed followed enhanced microhardness values and an improvement of the content of the nickel in the alloy. Annealing of all coatings at 200 °C revealed the crystallization of the matrix accompanied by a decrease of microhardness followed by stability for 24 h. The corrosion behavior of Zn–Ni/nano-TiO₂ composite coatings with various amount of particle content was mainly studied by electrochemical impedance spectroscopy in 3 % NaCl. It was seen that Zn–Ni/nano-TiO₂ composite coatings exhibited higher corrosion resistances comparing to Zn–Ni alloy coating and corrosion protection improved with increasing nano-TiO₂ in coatings.     

Properties of electroless and electroplated Ni–P and its application in microgalvanics

Composition, microstructure, surface morphology, mechanical properties and electrochemical behaviour of electroless (el) and electroplated (ep) Ni–P deposits are studied using XPS, SEM–EDX, AFM, nanoindentation measurements, cyclic voltammetry and capacitance measurements. Ni–P layers were compared with ep Ni films and bulk Ni. Ni–P layers prepared by both techniques contain 12–14 wt% phosphorus, present in oxidation states of P⁰ and P³⁻. El and ep Ni–P deposits are amorphous and are characterised by a relatively low average surface roughness (2 and 4 nm, respectively). The ep layers possess a rhythmic-lamellar microstructure indicating a periodic change of electrodeposition conditions. The el Ni–P layers do not show such laminated structure but exhibit small surface pores, which are absent in the ep layers. Comparable values for the hardness and the reduced elasticity modulus of el and ep coatings are determined from the nanoindentation data. The observed small differences indicate that the mechanical properties of Ni–P deposits depend not only on the phosphorus content but also on the deposit microstructure. Microelectrochemical measurements with the so-called droplet cell show that the electrochemical behaviour of both el and ep Ni–P coatings is practically identical and does not depend on the location on the sample surface. Evolution of O₂ and H₂ on Ni–P are similar to pure Ni (ep and bulk), but the corrosion resistance in acid solution is much better. The very similar properties and electrochemical behaviour of el and ep Ni–P deposits suggest that both materials are suitable for various applications in microsystem technology. For different substrates and microstructures of different size and geometry, deposition conditions have still to be optimised.     

Preparation and investigation of pulse co-deposited duplex nanoparticles reinforced Ni-Mo coatings under different electrodeposition parameters

In this work, Ni–Mo–SiC–TiN nanocomposite coatings were deposited on aluminium alloy by pulse electrodeposition with various electrodeposition parameters. The influences of the pulse frequency and duty cycle on the phase structure, morphology, mechanical and corrosion performance of the coatings were systematically investigated. The results showed that with increasing pulse frequency and decreasing duty cycle, the content of embedded duplex nanoparticles increased, and the grains refined gradually. The nanocomposite coating that was prepared at 20% duty cycle and 1000 Hz pulse frequency exhibited compact, uniform, and fine microstructures with the maximum incorporation of nanoparticles (6.81 wt% TiN and 1.72 wt% SiC). The wear rate and average friction coefficient then declined to 4.812 × 10^?4 mm³/N·m and 0.13, respectively, with a maximum microhardness of 519 HV. Simultaneously, the corrosion current density was reduced to 3.11 μA/cm², and a maximum impedance of 34888 Ω cm² was exhibited. The uniformly distributed duplex nanoparticles acted as a hindrance, which consequently supported the enhancement of corrosion and wear resistance. By investigating the variation of the pulse diffusion layer with electrical parameters, it was discovered that when the crystallite size is equivalent to or smaller than the diffusion layer thickness, it would be easier to cross the diffusion layer to incorporate in the coating. Additionally, the effects of various duty cycles and pulse frequencies on the nucleation process of the grains were discussed.     

Microstructures and properties of nickel-titanium carbide composites fabricated by laser cladding

In this work, Ni/TiC composites were synthesized by the laser cladding technique (LCT). A scanning electron microscope (SEM), X-ray diffractometer (XRD), microhardness meter, electrochemical workstation, and friction and wear tester examined the microstructure, surface morphology, phase structure, microhardness, wear, and corrosion resistances of the Ni/TiC composites. These results indicated the Ni/40TiC composite contained finer equiaxed crystals than the Ni and Ni/20TiC composites. In addition, numerous TiC particles in the Ni/40TiC composite impeded growth of the nickel crystals, which resulted in the fine microstructure of the Ni/40TiC composite. The Ni, Ni/20TiC, and Ni/40TiC composites exhibited face-centered cubic (f c c) lattices. The average microhardness values of the Ni/20TiC and Ni/40TiC composites were approximately 748 HV and 851 HV, respectively. The Ni/40TiC composite had the lowest friction coefficient (0.43) among all three coatings, and only some shallow scratches appeared on the surface of the Ni/40TiC composite. The corrosion potential (E) of Ni/40TiC exceeded the Ni/20TiC composite, and both were larger than the Ni composite, which indicated the Ni/40TiC composite had outstanding corrosion resistance and the Ni composite had poor corrosion resistance. The corrosion current densities (i) of Ni, Ni/20TiC, and Ni/40TiC composites were 5.912, 4.405, and 3.248 μA/cm², respectively.     

Pulse electrodeposition of Ni/nano-TiO<Subscript>2</Subscript> composites: effect of pulse frequency on deposits properties

Pure and composite nickel deposits containing nano-TiO₂ particles (d _m = 21 nm) were produced under direct-DC and pulse current-PC conditions. The influence of pulse frequency on the codeposition of TiO₂ particles, preferred orientation of Ni crystallites and grain size, as well as microhardness of the composites, was investigated systematically. Composites prepared in PC regime displayed higher incorporation percentage than those obtained under DC conditions, and the highest incorporation rates were achieved at pulse frequencies ν > 100 Hz. The application of pulse frequency accompanied by the embedding of TiO₂ nanoparticles in the nickel matrix resulted in a strong influence upon the crystalline orientation, the grain size and the corresponding microhardness. All composites exhibited higher microhardness values compared to the pure deposits, independent of the applied current conditions. Overall, when ascribing the observed strengthening effect of composites, not only grain refinement and dispersion strengthening mechanisms but also preferred crystalline orientation should be taken into consideration.     

Preparation and characterization of chromium deposits obtained from molten salts using pulsed currents

The electroplating of chromium from fused chloride electrolytes was investigated. The experimental conditions were defined taking into account the mechanisms of the electrochemical reduction of CrCl₂ and of the chromium nucleation and electrocrystallization phenomena. Chromium was plated on various substrates from concentrated LiCl–KCl–CrCl₂ (600 to 800 mol m^–3 CrCl₂) electrolyte. Direct or pulsed current electrolysis were carried out under a dry argon atmosphere in the 400 to 440 °C temperature range. The shape of the current signals was chosen, taking into account the chromium electrocrystallization phenomena onto a foreign substrate, so as to obtain well-defined structures for the chromium layers. The chromium deposits were characterized by SEM and EDX analysis, and by microhardness determination. Uniform chromium electroplates of high purity, high adherence with no cracks, were obtained by using pulsed current: signals with cathodic pulses and open-circuit periods preceded by cathodic pre-pulses. With this current shape, the mean rate of the chromium electroplating process remained lower than 10 m h^–1. However, using a repeated of periodic cathodic pre-pulse/cathodic pulse/anodic pulse/open circuit sequences, the growth rate of compact chromium layers increased to 100 m h^–1 or more.