Effect of electroless nickel interlayer on the electrochemical behavior of single layer CrN, TiN, TiAlN coatings and nanolayered TiAlN/CrN multilayer coatings prepared by reactive dc magnetron sputtering

The electrochemical behavior of single layer TiN, CrN, TiAlN and multilayer TiAlN/CrN coatings, deposited on steel substrates using a multi-target reactive direct current (dc) magnetron sputtering process, was studied in 3.5% NaCl solution. The total thickness of the coatings was about 1.5 μm. About 0.5 μm thick chromium interlayer was used to improve adhesion of the coatings. With an aim to improve the corrosion resistance, an additional interlayer of approximately 5 μm thick electroless nickel (EN) was deposited on the substrate. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) were used to study the corrosion behavior of the coatings. Scanning electron microscopy and energy dispersive X-ray analysis were used to characterize the corroded samples. The potentiodynamic polarization tests showed lower corrosion current density and higher polarization resistance (R_p) for the coatings with EN interlayer. For example, the corrosion current density of TiN coated steel was decreased by a factor of 10 by incorporating 5 μm thick EN interlayer. Similarly, multilayer coatings of TiAlN/CrN with EN interlayer showed about 30 times improved corrosion resistance as compared to the multilayers without EN interlayer. The porosity values were calculated from the potentiodynamic polarization data. The Nyquist and the Bode plots obtained from the EIS data were fitted by appropriate equivalent circuits. The pore resistance (R_pore), the charge transfer resistance (R_ct), the coating capacitance (Q_coat) and the double layer capacitance (Q_dl) of the coatings were obtained from the equivalent circuit. Multilayer coatings showed higher R_pore and R_ct values as compared to the single layer coatings. Similarly, the Q_coat and Q_dl values decreased from uncoated substrate to the multilayer coatings, indicating a decrease in the defect density by the addition of EN interlayer. These studies were confirmed by examining the corroded samples under scanning electron microscopy.     

Advanced anticorrosive coatings prepared from electroactive epoxy–SiO2 hybrid nanocomposite materials

A series of electroactive epoxy/amino-SiO₂ nanocomposite materials containing conjugated segments of electroactive amino-capped aniline trimer (ACAT) unit were successfully prepared. First of all, the amino-modified silica (AMS) particles of ∼50 nm in diameter were synthesized by performing the conventional base-catalyzed sol–gel reactions of tetraethyl orthosilicate (TEOS) in the presence of (3-aminopropyl)-trimethoxysilane (APTES) molecules. Subsequently, the AMS nanoparticles were blended into the epoxy ring-opening polymerization reactions between amino-terminated aniline trimer (ACAT)/T-403 and DGEBA, leading to the formation of electroactive epoxy resin–silica hybrid nanocomposites (EES). Furthermore, the redox behavior of as-prepared EES materials was identified by the electrochemical cyclic voltammetry studies. It should be noted that the as-prepared electroactive hybrid materials in the form of coating on cold-rolled steel (CRS) electrode were found to be much superior in corrosion protection over those of non-electroactive epoxy (NEE) and electroactive epoxy (EE) materials based on a series of electrochemical corrosion measurements in saline. The possible mechanism for the advanced enhancement of corrosion protection of EES coatings on CRS electrode could be interpreted as follows: (1) electroactive epoxy coatings may act as physical barrier coating; (2) redox catalytic capabilities of ACAT units existed in electroactive epoxy may induce the formation of passive metal oxide layers on CRS electrode, as further evidenced by SEM and ESCA studies; (3) well-dispersed AMS nanoparticles in EES matrix could act as effective hinder to enhance the oxygen barrier property of electroactive epoxy matrix, the result could be demonstrated by gas permeability analysis (GPA). Electroactive epoxy/SiO₂ nanocomposites were identified by a series of electrochemical measurements such as corrosion potential (E_corr), polarization resistance (R_p), corrosion current (I_corr) and electrochemical impedance spectroscopy (EIS) studied in 5 wt% NaCl electrolyte.     

Composite Ni/Al2O3 coatings and their corrosion resistance

Composite coatings Ni/Al₂O₃ were electrochemically deposited from a Watts bath. Al₂O₃ powder with particle diameter below 1 μm was codeposited with the metal. The obtained Ni/Al₂O₃ coatings contained 5-6% by weight of corundum. The structure of the coatings was examined by scanning electron microscopy (SEM). It has been found that the codeposition of Al₂O₃ particles with nickel disturbs the nickel coating's regular surface structure, increasing its microcrystallinity and surface roughness. DC and AC electrochemical tests were carried out on such coatings in a 0.5 M solution of Na₂SO₄ in order to evaluate their corrosion resistance. The potentiodynamic tests showed that the corrosion resistance of composite coating Ni/Al₂O₃ is better than that of the standard nickel coating. After 14 days of exposure the nickel coating corrodes three times faster than the Ni/Al₂O₃ coating. The electrochemical behaviour of the coatings in the corrosive solution was investigated by electrochemical impedance spectroscopy (EIS). An equivalent circuit diagram consisting of two RC electric circuits: one for electrode, nickel corrosion processes and the other for processes causing coating surface blockage, were adopted for the analysis of the impedance spectra. The changes in the charge transfer resistance determined from the impedance measurements are comparable with the changes in corrosion resistance determined from potentiodynamic measurements.     

Kinetics of hydrogen evolution reaction on nanocrystalline electrodeposited Ni62Fe35C3 cathode in alkaline solution by electrochemical impedance spectroscopy

Ternary nickel-iron-carbon (Ni-Fe-C) alloys have been characterized by means of microstructural and electrochemical techniques in view of their possible applications as electrocatalytic materials for hydrogen evolution reaction (HER). The electrochemical efficiency of the electrodes has been evaluated on the basis of electrochemical data obtained from the steady-state polarization Tafel curves, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) in 1 M NaOH solution at 298 K in the absence and presence of cyanide ion as the poison. Steady-state polarization Tafel curves showed that the Ni-Fe-C electrodes were apparently active for the HER. Therefore, the EIS studies were performed to obtain more precise data and find the source of activity. A surface roughness of more than three orders of magnitude was observed for Ni₆₂Fe₃₅C₃ electrode. The rate constants of the forward and backward reactions of Volmer and Heyrovský steps were estimated by using Tafel-impedance data. A comparison between the values obtained for R_f by the EIS and the values obtained for k₂ by approximation of Tafel-impedance data revealed that the increase in activity of Ni₆₂Fe₃₅C₃ electrode toward the HER was partially (20%) originated from increase in the surface roughness, and mostly (80%) from increase in the intrinsic activity.     

Synthesis of FePO4·xH2O for fabricating submicrometer structured LiFePO4/C by a co-precipitation method

Amorphous hydrated iron (III) phosphate has been synthesized by a coordinate precipitation method from equimolecular Fe(NO₃)₃ and (NH₄)₂HPO₄ solutions at an elevated temperature. Hydrated iron (III) phosphate samples and the corresponding LiFePO₄/C products were characterized by XRD and SEM. The electrochemical behavior was studied by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The LiFePO₄/C fabricated from as-synthesized FePO₄ delivered discharge capacities of 162.5, 147.3, 133.0, 114.7, 97.2, 91.3 and 88.5 mAh g⁻¹ at rates of 0.1C, 0.2C, 0.5C, 1C, 2C, 3C and 4C with satisfactory capacity retention, respectively.     

Effect of Ti amount on wear and corrosion properties of Ti-doped Al2O3 nanocomposite ceramic coated CP titanium implant material

Al₂O₃ and Ti-doped Al₂O₃ nanocomposite ceramic coatings were prepared by using a sol-gel dip-coating process. Corrosion and wear resistance of Al₂O₃ ceramic coatings in relation to Ti amount were carried out using pin-on-disk tribotester, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Surface characterizations before and after the corrosion and wear tests were investigated by the scanning electron microscope (SEM) and X-ray diffraction (XRD) and hardness analysis. The results of corrosion and wear tests exhibited that the corrosion and wear resistance of nanocomposite ceramic coatings became better than uncoated samples. Also, corrosion and wear resistance of nanocomposite ceramic coatings improved with Ti doping content increased.     

Advanced anticorrosive coatings prepared from electroactive polyimide-TiO2 hybrid nanocomposite materials

In this study, we present the first preparation and corrosion protection studies of a series of electroactive polyimide-TiO₂ (EPTs) hybrid nanocomposite materials containing conjugated segments of electroactive amino-capped aniline trimer (ATs) and TiO₂ nanoparticles of ∼10 nm in diameter. Redox behavior of as-prepared EPTs hybrid materials was identified by electrochemical cyclic voltammetry (CV) studies. Higher concentration of TiO₂ component in as-prepare corresponding EPTs was found to reveal better corrosion protection effect on cold-rolled steel (CRS) electrode based on sequential electrochemical corrosion measurements in 5 wt.% NaCl electrolyte. Enhancement of corrosion protection of EPTs coatings on CRS electrode could be interpreted by following three possible reasons: (1) Electroactive polyimide (EPI) could act as a physical barrier coating. (2) The redox catalytic capabilities of ATs units existed in EPTs may induce the formation of passive metal oxide layers on CRS electrode. (3) The well-dispersed TiO₂ nanoparticles in EPTs matrix could act as effective hinder to enhance the oxygen barrier property of EPTs.     

A study on the N-, S- and Cl-modified nano-TiO2 coatings for corrosion protection of stainless steel

Nano-titania coatings doped with anions of nitrogen, sulfur and chlorine have been supplied on the surface of 316L stainless steel by a sol-gel process and dip-coating technique. The measurements of XRD, SEM, ATR-IR, Raman and XPS were carried out to characterize the chemical composition and structure for the prepared samples. The corrosion performances of the coating in 0.5 M NaCl were evaluated by electrochemical impedance spectroscopy (EIS) and polarization measurements. According to the measurements of EIS and electrochemical polarization, the N-modified TiO₂ nano-coatings show a highest corrosion resistance among the prepared coatings. It is revealed, from the SEM, XRD and Raman characterizations, that the surface of N-modified TiO₂ nano-coatings are more compact and uniform, relatively well-crystallized and able to act as an optimal barrier layer to metallic substrates. The XPS analysis confirms the presence of low concentration of N element in two forms, atomic β-N (interstitial state) and chemisorbed γ-N₂ on the surface of TiO₂ nano-coatings. It is suggested that the addition of nitrogen is beneficial to improve the compact structure and enhance the hydrophobic property.     

Monitoring the degradation of a high solids epoxy coating by means of EIS and EN

This paper reports a study of the degradation processes suffered by steel samples painted with a high solid content epoxy coating. Because this coating shows a high resistance when exposed to NaCl solutions, HCl solutions were employed to accelerate the corrosion processes. Macroscopic images were used to observe the coating degradation. Then electrochemical techniques, electrochemical impedance spectroscopy (EIS) and electrochemical noise (EN) were employed to monitor the corrosion behaviour of the system studied. A close correlation was found between EIS and EN data. Several parameters were estimated using these techniques: R_po, R_ct, C_c, C_dl and Z_0.1 Hz using EIS, and R_n using EN. In addition, a new parameter estimated by means of EN was employed, Z_0.1 Hz(EN). The evolution of all these parameters with time enabled the effective monitoring of the degradation stage of the coating.     

Electrochemical impedance spectroscopy and corrosion behaviour of Al2O3-Ni nano composite coatings

In this paper, the results on the electrochemical impedance spectroscopy and corrosion properties of electrodeposited nanostructured Al₂O₃-Ni composite coatings are presented. The nanocomposite coatings were obtained by codeposition of alumina nanoparticles (13 nm) with nickel during plating process. The coating thickness was 50 μm on steel support and an average of nano Al₂O₃ particles inside of coatings at 15 vol.% was present. The structure of the coatings was investigated by scanning electron microscopy (SEM). It has been found that the codeposition of Al₂O₃ particles with nickel disturbs the nickel coating's regular surface structure. The electrochemical behavior of the coatings in the corrosive solutions was investigated by polarization potentiodynamic and electrochemical impedance spectroscopy methods. As electrochemical test solutions 0.5 M sodium chloride and 0.5 M potassium sulphate were used in a three electrode open cell. The corrosion potential is shifted to more negative values for nanostructured coatings in 0.5 M sodium chloride. The polarization resistance in 0.5 M sodium chloride decreases in 24 h, but after that increases slowly. In 0.5 M potassium sulphate solution the polarization resistance decreases after 2 h and after 30 h of immersion the polarization resistance is higher than that of the beginning value. The corrosion rate calculated by polarization potentiodynamic curves obtained after 30 min from immersion in solution is smaller for nanostructured coatings in 0.5 M potassium sulphate (4.74 μm/year) and a little bit bigger in 0.5 M sodium chloride (5.03 μm/year).     

Supersonic atmospheric plasma sprayed ZrO2 and ZrB2-SiC/ZrO2 coatings on Cf/Mg composites for anticorrosion

To improve the corrosion resistance of the carbon fiber reinforced magnesium matrix composites (C_f/Mg composites), ZrO₂ and ZrB₂-SiC/ZrO₂ composite coatings were prepared by supersonic atmospheric plasma spraying (SAPS) on C_f/Mg composites. The microstructure and phase composition of the coatings before and after the corrosion test were investigated. Open circuit potential and potentiodynamic polarization tests were measured at room temperature. Results revealed that the corrosion current density ($i_{\mathit{corr}}$) of the ZrO₂ coated C_f/Mg composites decreased by one order while the ZrB_2-SiC/ZrO₂ coated C_f/Mg composites reduced by two orders. Compared with C_f/Mg composites, the corrosion potential ($E_{\mathit{corr}}$) of the ZrO₂ and ZrB₂-SiC/ZrO₂ coated C_f/Mg composites increased by 220.5?mV and 1021.8?mV respectively, indicating that the ZrB₂-SiC/ZrO₂ composite coatings greatly improve the corrosion resistance of C_f/Mg composites. The uniform distribution of the SiC particles with small grain size in ZrB₂ is responsible for the densification of the coating. The ZrB₂-SiC/ZrO₂ composite coatings provide a barrier for the substrate to impede the entry of Cl^- in the corrosion solution, thus exhibiting a better corrosion resistance than the ZrO₂ coating.     

The influence of gun transverse speed on electrochemical behaviour of thermally sprayed Cr3C2-NiCr coatings in 0.5 M H2SO4 solution

In the present study, different types of 75% Cr₃C₂-25% NiCr coatings were applied on a steel substrate by means of high velocity oxygen fuel spraying (HVOF), and studied using ac and dc electrochemical measurements in an aerated and unstirred 0.5 M H₂SO₄ solution. Structural characterization was determined before and after electrochemical tests. Differences between all sprayed systems are related to the gun transverse speed and number of deposited layers, which strongly affected the electrochemical characteristics of the coated steels. The coating obtained with a higher torch speed showed better resistance against corrosion. The electrochemical impedance results were analyzed using an equivalent circuit where porosity of the coatings and substrate oxidation were considered.     

Epoxy coating with self-healing capability based on a 2-mercaptobenzothiazole-loaded CeO2 nanocontainer

In this study, we demonstrated a facile approach for the synthesis of nanocontainers using the encapsulation of a 2-mercaptobenzothiazole (MBT) inhibitor; these nanocontainers were capable of responsively releasing a corrosion inhibitor and of self-healing performances. The anticorrosive performance of the CeO₂ nanocontainers was investigated with electrochemical impedance spectroscopy (EIS) measurement in a saline electrolyte via the incorporation of different weight percentages (0.5, 1, and 2 wt %) of synthesized nanocontainer in epoxy (EP) resin. The EIS results show that the loading of 1 wt % CeO₂ nanocontainer containing MBT inhibitor in the epoxy (EP) coating [EP/NC MBT–CeO₂ (1%)] provided the highest R_coat, the lowest constant phase element of coating, and the optimum release of MBT at different operating pHs. The highest coating resistance R_coat values of this coating (7.81 × 10⁷ Ω cm²) were about 12 and 8573 times greater than those considered for EP–CeO₂ and EP coatings, respectively. Different releases of the MBT inhibitor were detected at various pHs. We found that the coating operating in acidic media exhibited a better self-healing performance. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47297.     

Resistance of metallic substrates protected by an organic coating containing glass flakes

The resistance against corrosion of an epoxy-polyamine-based coating immersed in a 3 wt.% sodium chloride solution was investigated by electrochemical impedance spectroscopy (EIS). The organic coating contained glass flakes as pigment in order to enhance its barrier characteristics. The data show that this coating is more strongly adhered and exhibits higher protection characteristics when applied onto carbon steel substrates than on galvanized steel. Though the capacitance of the coating (C_C) does not show any appreciable variation with immersion time, the resistance (R_PO) of the film is observed to increase with time upon immersion. The analysis of the data sustains that the organic film behaves as a porous, non-barrier coating. Two time constants are observed even at earlier exposures, and the improved corrosion resistance developed after the coating system was exposed to the test electrolyte is considered to originate from the precipitation of corrosion products within the pores in the film.     

Chemical composition and corrosion protection of silane films modified with CeO2 nanoparticles

The present work aims at understanding the role of CeO₂ nanoparticles (with and without activation in cerium(III) solutions) used as fillers for hybrid silane coatings applied on galvanized steel substrates.The work reports the improved corrosion protection performance of the modified silane films and discusses the chemistry of the cerium-activated nanoparticles, the mechanisms involved in the formation of the surface coatings and its corrosion inhibition ability.The anti-corrosion performance was investigated using electrochemical impedance spectroscopy (EIS), the scanning vibrating electrode technique (SVET) and d.c. potentiodynamic polarization. The chemical composition of silanised nanoparticles and the chemical changes of the silane solutions due to the presence of additives were studied using X-ray photoelectron spectroscopy (XPS) and nuclear magnetic resonance spectroscopy (NMR), respectively.The NMR and XPS data revealed that the modified silane solutions and respective coatings have enhanced cross-linking and that silane-cerium bonds are likely to occur.Electrochemical impedance spectroscopy showed that the modified coatings have improved barrier properties and the SVET measurements highlight the corrosion inhibition effect of ceria nanoparticles activated with Ce(III) ions. Potentiodynamic polarization curves demonstrate an enhanced passive domain for zinc, in the presence of nanoparticles, in solutions simulating the cathodic environment.     

Corrosion Investigation of Chromium Nitride and Chromium Carbide Coatings for PEM Fuel Cell Bipolar Plates in Simulated Cathode Condition

Transition metals nitrides and carbides are used as coatings on bipolar plates for proton exchange membrane fuel cells (PEMFCs) due to their suitable electrical conductivity and corrosion resistance. Chromium electroplated AISI 316L stainless steel bipolar plates were treated by plasma nitriding and solid carburizing to form chromium nitride and chromium carbide, respectively. The presence of CrN/Cr₂N and Cr₇C₃/Cr₂₃C₆ was verified by X‐ray diffractometry (XRD) in chromium nitride and chromium carbide coatings, respectively. The corrosion behavior of coatings was investigated by potentiodynamic polarization, potentiostatic polarization and electrochemical impedance spectroscopy (EIS) in simulated cathode condition. Coated samples showed better corrosion behavior than untreated bare sample. EIS results indicated decrease in corrosion current density after 500 hours, however coatings acted as barrier against solution access to substrate. Corrosion current densities of coatings were close to targets of United Stated department of energy (DOE).     

Electrochemical impedance studies of modified Ni-P and Ni-Cu-P deposits in alkaline medium

Ni-P and Ni-Cu-P deposits were supported over the commercial carbon using the electroless plating technique. The formed samples were characterized by applying SEM, XRD and EDX analyses. An amorphous Ni-P surface was obtained with 73.70 wt% Ni and 11.45 wt% P. The addition of copper to the plating bath reduces the deposited amount of nickel and phosphorus. The electrochemical performance of these deposits has been investigated in 0.1 M KOH solution using electrochemical impedance spectroscopy (EIS) measurements. The effect of pH, deposition time and temperature of the plating bath on the impedance characteristics of the two deposits was studied. It was found that the resistance (R_T) and relative thickness (1/C_T) of the two coatings in 0.1 M KOH solution increase with increasing either pH or deposition time or temperature of the plating bath. Our results indicate that Ni-Cu-P deposit has more corrosion resistance and lower corrosion current density (i_corr) value than Ni-P deposit under different conditions. EIS results were well confirmed by potentiodynamic polarization and cyclic voltammetry techniques.     

Tribocorrosion behaviour of TiCxOy thin films in bio-fluids

Decorative coatings require not only an attractive appearance for market applications, but also an ability to protect the surface underneath. Because of this, corrosion, wear and their combined effects (termed tribocorrosion) are particularly important for lifetime prediction. In this paper, the tribocorrosion behaviour of a range of single layered titanium oxycarbide, TiC_xO_y, coatings, produced by DC reactive magnetron sputtering, has been studied and reported as a function of electrode potential and applied load. The study was conducted in a reciprocating sliding tribo-system (Plint TE 67/E) in a bio-fluid (an artificial perspiration solution) at room temperature. During the wear tests, both the open-circuit potential and the corrosion current were monitored. The results showed that electrode potential and load have a significant influence on the total material loss. The variations in R_p (polarization resistance) and C_f (capacitance) before and after sliding, obtained by Electrochemical Impedance Spectroscopy (EIS) were evaluated in order to provide an understanding of the resistance of the film in such conditions. Tribocorrosion maps were generated, based on the results, indicating the change in mechanisms of the tribological and corrosion parameters for such coatings, as a function of load and applied potential.     

Corrosion behavior of SM 80SS tube steel in stimulant solution containing H2S and CO2

Scanning electron microscopy, X-ray diffraction and electrochemical measurement technique were applied to investigate the corrosion of SM 80SS tube steel in stimulant solution with carbon dioxide (CO₂) and hydrogen sulfide (H₂S) at variable conditions of PCO₂/PH₂S and temperature. The results suggest that there exists a synergism of sweet corrosion and sour corrosion on the steel surface, corrosion attack increases in the initial stage and then decrease with the increase of PCO₂ or PH₂S; serious corrosion occurs in the PCO₂/PH₂S ranged from 31 to 520. In addition, the fitted parabola function equation Y = 0.47873 + 0.04014X - (3.23788E−5)X² is established, and the most serious corrosion is 600 for PCO₂/PH₂S. Under the moderate contents of PCO₂ and PH₂S, the corrosion scale consists of FeS_0.9 and FeCO₃; for relatively high PH₂S, additive product FeS comes into being at high temperature such as T = 150 °C, product FeO(OH) is found in the corrosion scale. The H₂S corrosion has a significant effect on the whole reaction process and iron sulfide is superior to precipitating on the steel surface compared with iron carbonate. In addition, the surface scales of iron sulfide almost act as a diffusion barrier and inhibit the corrosion by a coverage effect strongly depending on H₂S concentration by EIS measurement.     

Using electrochemical impedance spectroscopy to predict the corrosion resistance of unexposed coated metal panels

The goal of the current work was to determine if electrochemical impedance spectroscopy (EIS) testing of a series of coated but unexposed metal panels could predict the corrosion results of other sections of the same coated panels that were subjected to both continuous and cyclic corrosion testing. Variables included metal, pretreatment, primer, and topcoat. EIS results were shown to be strongly dependent upon the time-of-residence in the electrochemical cell prior to commencement of testing, and to the choice of electrolyte used in the cell. Good correlations between EIS and corrosion testing were seen for topcoat effects, but not for pretreatment effects. EIS results appear to relate mostly to barrier properties rather than electrochemical properties of coatings. It is suggested that the variation seen in EIS solution resistance values (R_s) can be utilized to quantify total system error. Total error was estimated by three techniques: total R_s variation, panel replicate variation, and EIS reading replication. The three approaches yielded similar results: total error for equivalent circuit components expressed in log₁₀ form was on the order of 50%, expressed as percent standard deviation.