Properties of electrodeposited nanocrystalline Ni-B alloy films

The influence of the boron content on the various properties of nanocrystalline Ni-B alloy produced by electrodeposition was investigated. The considerable reduction in grain size was observed with increasing boron content. The internal stress was tensile and increased linearly with increasing boron content. Hardness increased up to 750 Hv at 2 at.% boron and then kept the value to 11 at.% boron for as-plated Ni-B coatings.The hardness of Ni-B films increased considerably due to the intermetallic Ni₃B precipitation by the heat treatment and maximum hardness of each coating increases with boron content. Wear resistance decreased with increasing the boron content because of high friction coefficient and brittle fracture of coating with high content of boron.     

Synthesis and characterization of poly(aniline) and poly(o-anisidine) films in sulphamic acid solution and their anticorrosion properties

Poly(o-anisidine) (POA) and polyaniline (PANI) coatings were synthesized on platinum (Pt) surface and stainless steel (SS) in monomer containing 0.50 M sulphamic acid (SA) solution by means of cyclic voltammetry (CV) technique. Meanwhile, poly(o-anisidine) film was also deposited with a different scan rate on SS electrode. The behaviour of PANI and POA films obtained on stainless steel examined by CV was different from the one obtained for PANI and POA on Pt electrode. The corrosion performances of PANI and POA coatings in 3.5% NaCl solution were investigated with anodic polarization technique and electrochemical impedance spectroscopy (EIS). EIS measurements verified the effect of monomers and that of scan rate on corrosion inhibition of coatings on SS electrode. The results showed that POA film synthesized at low scan rate exhibited an effective anticorrosive property on SS electrode. POA synthesized at low scan rate and PANI coatings provided a remarkable anodic protection to SS substrate for longer exposure time than the one observed for POA coating produced at high scan rate as well as that of bare SS electrode.     

Electrochemical studies on electroless ternary and quaternary Ni-P based alloys

The autocatalytic (electroless) deposition of Ni-P based alloys is a well-known commercial process that has found numerous applications because of their excellent anticorrosive, wear, magnetic, solderable properties, etc. It is a barrier coating, protecting the substrate by sealing it off from the corrosive environments, rather than by sacrificial action. The corrosion resistance varies with the phosphorus content of the deposit: relatively high for a high-phosphorus electroless nickel deposit but low for a low-phosphorus electroless nickel deposit. In the present investigation ternary Ni-W-P alloy films were prepared using alkaline citrate-based bath. Quaternary Ni-W-Cu-P films were deposited by the addition of 3 mM copper ions in ternary Ni-W-P bath. X-ray diffraction (XRD) studies indicated that all the deposits were nanocrystalline, i.e. 1.2, 2.1 and 6.0 nm, respectively, for binary, ternary and quaternary alloys. Corrosion resistance of the films was evaluated in 3.5% sodium chloride solution in non-deaerated and deaerated conditions by potentiodynamic polarization and electrochemical impedance (EIS) methods. Lower corrosion current density values were obtained for the coatings tested in deaerated condition. EIS studies showed that higher charge transfer resistance values were obtained for binary Ni-P coatings compared to ternary or quaternary coatings. For all the coatings a gradual increase in the anodic current density had been observed beyond 740 mV. In deaerated condition all the reported coatings exhibited a narrow passive region and all the values of E_p, E_tp and i_pass were very close showing no major changes in the electrochemical behavior. In the non-deaerated conditions no passivation behavior had been observed for all these coatings.     

Improved electrochemical performance of trivalent-chrome coating on Al 6063 alloy via urea and thiourea addition

This project aims at improving the electrochemical performance of trivalent-chrome coating through urea and thiourea addition. The electrochemical behaviors of coatings formed with different concentrations of urea and thiourea were investigated in 3.5 wt.% NaCl solution at 25 °C, using potentiodynamic polarization curves and EIS. The corrosion resistance of coatings is improved greatly by adding a small amount of inhibitors, whereas the excessive addition deteriorates the corrosion resistance. Thiourea addition presents better effect than urea. To explain the EIS results of the coatings, a simple equivalent circuit was designed. The EIS parameters were obtained by fitting the EIS plots. The results of the polarization curves and EIS show that the inhibitor-containing coatings present better corrosion resistance than the coating without inhibitor. The morphology and composition and valence state of the conversion coatings were examined by SEM and EDS and XPS, respectively. The results indicated that the trivalent chromium coating was developed on Al 6063 alloy, urea and thiourea inhibitors were also deposited on the substrates, respectively. A noticeable chemical shift was also observed.     

Corrosion protection with zinc-rich epoxy paint coatings embedded with various amounts of highly dispersed polypyrrole-deposited alumina monohydrate particles

Active anodic zinc content below 90 wt.% does not support sufficient electrical contacts but higher contents cause high porosity of traditional liquid zinc-rich paints (ZRPs). To resolve this problem, our proposal is the application of highly dispersed polypyrrole (PPy) coated alumina inhibitor particles (PCAIPs) in zinc-rich paint compositions. Using these nano-size inhibitor particles at concentrations from 4.55 to 0.85 wt.%, hybrid paints were formulated with zinc contents ranging from 60 to 85 wt.% at the same time. Submicron morphology and nano-scale structure, spectroscopy characteristics and electrochemical properties of the PCAIPs were studied by transmission electron microscopy (TEM) and rheology, Fourier-transform infrared spectroscopy (FT-IR) and cyclic voltammetry (CV) in first part of the work. In the second part, electrolytic corrosion resistivity of two sets of paint coatings were salt-spray chamber and immersion tested with 5 wt.% aqueous solution of sodium chloride. Active corrosion prevention ability of the salt-spray tested coatings was evaluated in compliance with ISO recommendations. Dielectric properties of the coatings during the immersion tests were monitored by electrochemical impedance spectroscopy (EIS). Corrosion tested area of the coatings was investigated by glow-discharge optical emission spectroscopy (GD-OES) to disclose infiltration of corrosive analytes and oxygen enrichment in the cross-section of the primers in comparison with their pristine states. Morphology of the zinc pigments was examined by scanning electron microscopy (SEM), and quality of steel specimens and the interfacial binder residues by X-ray photoelectron spectroscopy (XPS) as well as FT-Raman and Mössbauer spectroscopy. The results of both types of corrosion tests evidenced efficient utilisation of sacrificial anodic current for galvanic protection and improved barrier profile of the hybrid coatings, along with the PCAIP inhibited moderate self-corrosion of zinc. As a result of well balanced active/passive function, the hybrid coating containing zinc at 80 wt.% and PCAIPs at 1.75 wt.% embedding PPy at 0.056 wt.% indicated the most advanced corrosion prevention. Galvanic function of the hybrid paints is interpreted on the basis of size-range effect and spatial distribution of the alumina supported PPy inhibitor particles and basic electrical percolation model considerations.     

Effective corrosion protection of AA6061 aluminum alloy by sputtered Al-Ce coatings

Al-Ce coatings were deposited on silicon and AA6061 aluminum alloy substrates by DC magnetron sputtering using aluminum in combination with pure cerium targets. The materials were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and electrochemical impedance spectroscopy (EIS) in order to consider their application as high corrosion resistance coatings. The corrosion behavior of the films was studied using a NaCl aqueous solution (3.5 wt%). As for the characterization results, an apparent amorphous phase of aluminum oxide with small cerium compounds embedded in the matrix was detected by the X-ray diffraction patterns and HRTEM on the deposited films at 200 W and 4 Pa. At these conditions, AFM and SEM images evidenced crack-free coatings with low-roughness nanometric structures and columnar growth. EIS and Tafel results converged to indicate an inhibition of the corrosion reactions. The film displayed good stability in the aggressive medium and after 1 day of exposure underwent very little degradation. The variations in the impedance and Tafel characteristics were found to occur as a function of cerium content, which provokes important changes in the film protective properties.     

Sol-enhanced electroplating of nanostructured Ni-TiO2 composite coatings—The effects of sol concentration on the mechanical and corrosion properties

Novel sol-enhanced Ni-TiO₂ nano-composite coatings were electroplated by adding a transparent TiO₂ sol into the traditional electroplating Ni solution. It was found that the structure, mechanical properties and corrosion resistance of the nano-composite coatings were largely determined by the sol concentration. The higher sol concentration in the plating electrolyte led to a higher content of TiO₂ nano-particles in the coating matrix. The coating prepared at the sol concentration of 12.5 mL/L had the best microhardness, wear resistance and corrosion resistance. Adding excessive sol to the electrolyte changed the surface microstructure, caused cracking on the coating surface and deteriorated the properties. It was demonstrated that the corrosion resistance of the composite coatings is determined by two factors: surface microstructure and incorporation of TiO₂ nano-particles.     

Zinc deposited polymer coatings for copper protection

Polypyrrole (PPy) and polyaniline (PAni) coatings were electrosynthesized on copper, by using cyclic voltammetry technique. Then, these coatings were modified with the deposition of zinc particles from aqueous zinc sulphate solution. The electrodeposition of zinc was achieved at a constant potential value of −1.20 V, in the amount of ∼0.75 mg/cm². The corrosion performance of zinc modified polymer coatings were investigated in 3.5% NaCl solution; by using the electrochemical impedance spectroscopy (EIS), and anodic polarization curves. The zinc particles improved the barrier property of polymer films, thanks to formation of voluminous zinc corrosion products within the pores of polymer coating. Also, the zinc particles provided cathodic protection to the substrate, where the polymer film played the role of conductance between zinc particles and copper.     

Tribological and electrochemical behavior of thick Cr-C alloy coatings electrodeposited in trivalent chromium bath as an alternative to conventional Cr coatings

Alternative process to hexavalent chromium plating, substitute materials and new designs are urgently needed owing to the requirement of “clean” manufacture. This comparative study was conducted to systematically investigate the tribological and electrochemical behavior of the Cr-C alloy coatings electrodeposited from a trivalent chromium bath and the hard Cr coatings electrodeposited from conventional hexavalent chromium bath, using reciprocating ball-on-disc tribometer and electrochemical analyzer. The electroplated Cr-C alloy coatings with thickness of 50 μm and acceptable quality that can be used for wear resistance as well as corrosion resistance purposes were produced successfully. The results show that the as-deposited Cr-C alloy coatings exhibited crack-free surface and amorphous/microcrystalline structure. The following heat treatment resulted in the cracked surface and the increase in hardness for the electroplated Cr-C alloy coatings. In contrast, the conventional Cr coatings exhibited cracked surface and their hardness decreased with the increase in annealing temperature. The electroplated Cr-C alloy coatings after heat treatment at 200 °C for 1 h exhibited better wear resistance than the conventional Cr coatings. In regard to the electrochemical behavior, the as-deposited Cr-C alloy coatings exhibited better corrosion resistance than the conventional Cr coatings. Therefore, the electroplated Cr-C alloy coatings are environmentally acceptable candidates to replace the conventional Cr coatings.     

Poly(N-ethylaniline) coatings on 304 stainless steel for corrosion protection in aqueous HCl and NaCl solutions

Poly(N-ethylaniline) (PNEA) coatings were grown by potentiodynamic synthesis technique on 304 stainless steel (SS) alloy from 0.1 M of N-ethylaniline (NEA) in 0.3 M oxalic acid solution. Characterization of adhesive and electroactive PNEA coatings was carried out by cyclic voltammetry, FT-IR spectroscopy and scanning electron microscopy (SEM) techniques. The protective properties of PNEA coatings on SS were elucidated using linear anodic potentiodynamic polarization, Tafel and electrochemical impedance spectroscopy (EIS) test techniques, in highly aggressive 0.5 M HCl and 0.5 M NaCl solutions. Linear anodic potentiodynamic polarization test results proved that PNEA coating improved the degree of protection against pitting corrosion in HCl and NaCl solutions. Tafel test results showed that PNEA coating appears to enhancement protection for SS in 0.5 M NaCl and 0.5 M HCl solutions. However, according to long-term EIS results, PNEA coating is better for the protection of SS electrodes during the long immersion period in NaCl compared to that in HCl medium.     

Anticorrosive properties of polypyrrole films modified with zinc onto SAE 4140 steel

Polypyrrole (PPy) films modified with zinc were electrosynthesized onto SAE 4140 steel in presence of bis(2-ethylhexyl) sulfosuccinate (AOT). The Zn and PPy electrodeposition was realized by using cyclic voltammetry at different temperatures. The corrosion protection properties of the films were examined in chloride solution by open circuit measurements, linear polarization and electrochemical impedance spectroscopy (EIS). The obtained results indicate that the presence of Zn in the polymer matrix improves the anticorrosive performance of PPy films. The best anticorrosion efficiency was obtained for the coatings modified at 20 °C which provided anodic protection to the steel substrate for a long period of immersion in chloride solution. Cathodic protection was observed when the electrodeposition temperature was increased. Adherence and anticorrosive properties declined sharply for the coatings electrosynthesized at 5 °C.     

Evaluation of the corrosion resistance of phosphate coatings obtained by anodic electrochemical treatment

The corrosion resistance of phosphate coating obtained by anodic electrochemical treatment at 4–6 mA/cm² is addressed in this paper. The corrosion performance of these coatings is also compared with the coatings obtained by chemical treatment. The regenerated phosphoric acid under the influence of anodic current causes a large variation in morphological features of the coatings. Immersion and salt spray tests indicate the ability of these coatings to act as a barrier film on mild steel. Polarization and electrochemical impedance spectroscopic (EIS) studies indicate that the corrosion resistance of phosphate coatings obtained by anodic treatment decreases with increase in current density employed for deposition. In spite of their higher coating weight, the corrosion resistance of phosphate coatings obtained by anodic treatment is inferior to those obtained by chemical treatment. The porosity or discontinuities created due to the dissolution of the coating under the influence of anodic current are considered responsible for the inferior corrosion resistance of these coatings. The study concludes that anodic treatment has only a limited scope for preparing phosphate coatings with improved corrosion resistance.     

Electrochemical behavior of centrifuged cast and heat treated Ti-Cu alloys for medical applications

The aim of this study was to evaluate the general electrochemical corrosion resistance of Ti-5, 7.1 and 15 wt.% Cu alloys with a view to medical applications. A centrifuged casting set-up and a solution heat treatment at 900 °C for 2 h were used to prepare the samples. Electrochemical impedance spectroscopy (EIS) and potentiodynamic anodic polarization techniques were used to analyze the corrosion resistance in a 0.15 M NaCl solution at 25 °C. An equivalent circuit analyses was also conducted. It was found that the corrosion rate increased with increasing Cu content. The results have shown that the addition of Cu has not stabilized the β phase. Martensite and Ti₂Cu intermetallic particles provided by casting and heat treatment processes, respectively, have important roles on the resulting impedance parameters and passive current densities of the Ti-Cu alloys.     

Effect of 2-amino-3-mercaptopropanoic acid (cysteine) on the corrosion behaviour of low carbon steel in sulphuric acid

The effect of cysteine (cys) on the corrosion of low carbon steel (LCS) in sulphuric acid solution was investigated using electrochemical and scanning electron microscopy (SEM) techniques. Electrochemical impedance spectroscopy (EIS) results reveal that the presence of cys at low concentrations (0.1-0.5 mmol L⁻¹) promoted the LCS corrosion process, whereas an inhibiting effect was observed at higher concentrations (1.0-5.0 mmol L⁻¹), which was enhanced on deaeration of the test solution. Polarization results revealed that cys actually inhibited the cathodic process at all concentration but exerted a stimulating effect on the anodic metal dissolution reaction. Despite the cathodic inhibiting effect, the polarization resistances at low cys concentrations were less than that in the blank acid. This suggests that the anodic reaction was the predominant influence determining the corrosion rates in the presence of cys. This has been discussed vis-à-vis the catalytic effect of the Fe-cys complex, which turns the Fe surface more electrochemically active.     

Studying the corrosion protection properties of an epoxy coating containing different mixtures of strontium aluminum polyphosphate (SAPP) and zinc aluminum phosphate (ZPA) pigments

Epoxy/polyamide coatings were loaded with different mixtures of strontium aluminum polyphosphate (SAPP) and zinc aluminum phosphate (ZPA) pigments. Moreover, a coating containing zinc phosphate (ZP) was prepared as a reference sample. The coatings were applied on St-37 steel substrates and then were exposed to 3.5 wt% NaCl solution up to 35 days. The corrosion inhibition properties of the pigments extracts were studied on bare steel samples by a potentiodynamic polarization technique after 24 h immersion. The morphological properties and corrosion resistance of the coatings were investigated by scanning electron microscope (SEM), optical microscope, electrochemical impedance spectroscopy (EIS) and salt spray tests.     

A study of the corrosion resistance of a waterborne acrylic coating modified with nano-sized titanium dioxide

The incorporation of nano-sized inorganic pigment particles into organic coatings may offer the potential for improving many of their properties, including corrosion resistance, at relatively low loadings. In the present research, titanium dioxide with a crystallite size of 5-10 nm was added to a waterborne organic primer formulation at loadings from 0.1 to 5% (w/w) and applied to hot-dip galvanized steel (HDG) panels. The corrosion resistance of the modified coatings was measured by neutral salt spray corrosion testing and electrochemical impedance spectroscopy (EIS), with an unpigmented film tested for comparison. 3% (w/w) TiO₂ appeared to produce an optimum improvement in the corrosion resistance.     

Formation of anodic films on sputtering-deposited Al-Hf alloys

The growth of barrier-type anodic films at high efficiency on a range of sputtering-deposited Al-Hf alloys, containing from 1 to 95 at.% Hf, has been investigated in ammonium pentaborate electrolyte. The alloys encompassed nanocrystalline and amorphous structures, the latter being produced for alloys containing from 26 to 61 at.% Hf. Except at the highest hafnium content, the films were amorphous and contained units of HfO₂ and Al₂O₃ distributed relatively uniformly through the film thickness. Boron species were confined to outer regions of the films. The boron distributions suggest that the cation transport number decreases progressively with increasing hafnium concentration in the films, from ∼0.4 in anodic alumina to ∼0.2 for a film on an Al-61 at.% Hf alloy. The distributions of Al³⁺ and Hf⁴⁺ ions in the films indicate their similar migration rates, which correlates with the similarity of the energies of Al³⁺-O²⁻ and Hf⁴⁺-O²⁻ bonds. For an alloy containing ∼95 at.% Hf, the film was largely nanocrystalline, with a thin layer of amorphous oxide, of non-uniform thickness, at the film surface. The formation ratios for the films on the alloys changed approximately in proportion to the hafnium content of the films between the values for anodic alumina and anodic hafnia, ∼1.2 and 1.8 nm V⁻¹ respectively.     

Studies on plasma sprayed bi-layered ceramic coating on bio-medical Ti-13Nb-13Zr alloy

Biomedical Ti alloys are prone to undergo degradation due to the combined effect of wear and corrosion. To overcome these problems, surface modification techniques are being used. In this paper, the biomedical Ti alloy Ti-13Nb-13Zr was plasma sprayed with nanostructured Al₂O₃-13 wt%TiO₂, yttria stabilized zirconia powders and bilayer containing alternate layers of the two coatings to improve the corrosion resistance and microhardness of the substrate. The plasma sprayed coatings were characterized by X-ray diffraction, scanning electron microscopy and Raman spectroscopy. The microstructure, microhardness and surface roughness of the coatings were investigated. The corrosion resistance of the coatings was studied in simulated body conditions. The results show improved corrosion resistance for the bilayered coating compared to the individual plasma sprayed coatings on biomedical Ti-13Nb-13Zr alloy substrate.     

Influence of electrochemical potential on the tribocorrosion behaviour of high carbon CoCrMo biomedical alloy in simulated body fluids by electrochemical impedance spectroscopy

The corrosion and tribocorrosion behaviour of a high carbon CoCrMo alloy sliding against alumina in simulated body fluids under potentiostatic conditions was investigated. The electrochemical behaviour of the sample in two electrolytes at different potentials (−1 V_Ag/AgCl, −0.5 V_Ag/AgCl, +0.05 V_Ag/AgCl, +0.5 V_Ag/AgCl and +0.75 V_Ag/AgCl) was studied by means of electrochemical impedance spectroscopy (EIS). The effects of solution chemistry and applied potential on the wear volume and anodic current were determined. Result shows that wear of CoCrMo alloy is negligible under cathodic and in the cathodic-anodic transition and considerably increases in the passive domain. Third body behaviour depends on surface chemistry which also varied depending on solution chemistry and electrochemically applied potential thus, modifies the tribocorrosion rate of CoCrMo alloy.     

Corrosion protection of steel by sulfo-doped polyaniline-pigmented coating

This work presents the corrosion protection behaviour of mild steel in neutral saline conditions (salt spray/immersion) by using coatings based on chlorinated rubber and benzene-sulfonate (BS) or lignosulfonate (LS)-doped polyaniline (PANI). Standardized accelerated (salt spray) and immersion tests were performed to assess the protective performance of the coatings. Analysis and interpretation of the experimental data (i.e., EIS, potentiodynamic data and visual observations) showed that both PANI-BS and PANI-LS inhibit corrosion of painted steel exposed to a 3.5% NaCl solution. Among the tested concentrations (0.5, 1.5 and 3 wt.%), the greatest inhibition was observed at low concentration of PANI-BS (0.5%). Samples with higher PANI-BS loadings (1.5 and 3%) appear severely corroded after 560 h of salt spray exposure, which was related to the release of corrosive benzene sulfonic acid. On the contrary, the coatings with lignosulfonate doped PANI performed well both in the salt spray and immersion tests, especially at the highest PANI concentrations (1.5 or 3%). With regard to the healing properties, PANI-LS with the lowest conductivity (1 S cm⁻¹) performed the best.