Corrosion resistance of phosphate coatings obtained by cathodic electrochemical treatment: Role of anode–graphite versus steel

The formation of phosphate coatings by cathodic electrochemical treatment using graphite and steel anodes and evaluation of their corrosion resistance is addressed in this paper. The type of anode used, graphite/steel, has an obvious influence on the composition of the coating, resulting in zinc–zinc phosphate composite coating with graphite anode and zinc–iron alloy–zinc phosphate–zinc–iron phosphate composite coating with steel anode. The corrosion resistance of the coating is found to be a function of the composition of the coating. The deposition of zinc/zinc–iron alloy along with the zinc phosphate/zinc and zinc–iron phosphate using graphite/steel anodes has caused a cathodic shift in the E_corr compared to uncoated mild steel substrates. The i_corr values of these coatings is very high. EIS studies reveal that zinc/zinc–iron alloy dissolution is the predominant reaction during the initial stages of immersion. Subsequently, the formation of zinc and iron corrosion products imparts resistance to the charge transfer process and increases the corrosion resistance with increase in immersion time. The corrosion products formed might consist of oxides and hydroxychlorides of zinc and iron. The study suggests that cathodic electrochemical treatment could be effectively utilized to impart the desirable characteristics of the coating by choosing appropriate anode materials, bath composition and operating conditions.     

Phenol electropolymerization on phosphated mild steel via zinc electrodeposition

Phenol electropolymerization to polyoxyphenylene coatings on phosphated steel and phosphated galvanized steel, normally impossible under the conditions allowing effective coating formation on either steel or zinc, is activated by cathodic deposition of zinc. A critical zinc amount has been found to be necessary to suppress electrochemical processes competitive with electropolymerization and induce coating formation with nearly 100% efficiency. SEM analysis showed that this critical amount of zinc corresponded to the formation of a low number of zinc nuclei emerging at the surface of the phosphate layer, on which, however, polyoxyphenylene was formed as a continuous coating. A.c. impedance tests showed that initial barrier properties are worse for coatings grown on zinc-plated phosphated samples than for those grown on steel from the same solutions. However, the long term corrosion resistance is much better in the former case, the improvement being largely associated with zinc cathodic protection     

The improvement of anticorrosion properties of zinc-rich organic coating by incorporating surface-modified zinc particle

The corrosion behaviors of zinc-rich coating with various zinc contents, ranging from 0 to 60 volume percent, in thin organic coatings (below 5 μm) were characterized by electrochemical impedance spectroscopy (EIS), free corrosion potential (E_corr) measurement and cycle corrosion test (CCT). It was verified that both coatings with 60 volume percent of zinc powder and without zinc powder showed good corrosion resistance mainly due to the cathodic protection and barrier effect, respectively. On the other hand, coatings with an intermediate concentration (10–40 vol.%) of zinc powder was not successful in protecting a steel substrate efficiently. To improve anticorrosion property of zinc-rich coating, the surface modification of zinc particle was carried out with derivatives of phosphoric and phosphonic acid in the aqueous solution. The effects of the surface modification of zinc particle on corrosion resistance of the coating were investigated with scanning vibrating electrode technique (SVET) and X-ray photoelectron spectroscopy (XPS). The best anti-corrosion performance was achieved when the incorporated zinc particle was treated with phosphoric acid 2-ethylhexyl ester and calcium ion simultaneously, which induced the formation of alkyl-phosphate-calcium complex layer of 190 nm in thickness on zinc particles. Corrosion resistance was improved by the decreased zinc activity and the increased compatibility between the formed complex layer on zinc surface and polymer binder matrix.     

Conducting polymer based hybrid nano-composites for enhanced corrosion protective coatings

Hybrid composite coatings containing zinc oxide (ZnO) and polyaniline (PANI) as nano-additives dispersions were prepared with poly(vinyl acetate) (PVAc) as the major matrix. The steel plates dip-coated with these formulations were tested for corrosion protection by immersion in saline water over long periods. The Tafel plots for the determination of open circuit potential (OCP) and corrosion current (I_corr) were recorded. The coatings containing both ZnO and PANI showed improved corrosion resistance as compared to the single component coating. The I_corr values of PVAc–ZnO–PANI are found to be two-order magnitude lower than that of PVAc and PVAc–ZnO coatings. The results are explained on the basis of enhancement in barrier properties due to nano-particulate additives in PVAc–ZnO–PANI film together with the redox behaviour of PANI and protective oxide layer formation near the substrate.     

Corrosion behavior of carbon steel coated with magnesium electrodeposited from methyl magnesium chloride solution

Magnesium coating was electroplated on carbon steel to improve its corrosion protection. The analytical characterization of the magnesium coating was performed by scanning electron spectroscopy and energy dispersive X-ray spectroscopy. The electrochemical behavior of Mg-coated carbon steel was assessed by electrochemical impedance spectroscopy, open-circuit potential measurements and potentiodynamic polarization curves in 0.03% sodium chloride solution. The electrochemical results showed that the self-corrosion current density (i _corr) of magnesium-coated steel was 0.32 mA cm^?2 (about 1.8% of that of uncoated steel). Impedance results showed an increase of the total impedance when magnesium coating was applied on steel substrate. The corrosion protection was ensured by a two-step mechanism. The first step was cathodic polarization; the second step was the formation of a barrier due to magnesium oxides composed of MgO, Mg(OH₂) and Mg(OH₃)Cl.     

Corrosion stability of polyester coatings on steel pretreated with different iron–phosphate coatings

The influence of steel surface pretreatment with different types of iron–phosphate coatings on the corrosion stability and adhesion characteristics of polyester coatings on steel was investigated. The phosphate coating was chemically deposited either from the simple novel plating bath, or with the addition of NaNO₂, as an accelerator in the plating bath. The morphology of phosphate coatings was investigated using atomic force microscopy (AFM). The corrosion stability of polyester coatings on steel pretreated by iron–phosphate coatings was investigated by electrochemical impedance spectroscopy (EIS) in 3% NaCl solution, while “dry” and “wet” adhesion were measured by a direct pull-off standardized procedure. It was shown that greater values of pore resistance, R_p, and smaller values of coating capacitance of polyester coating, C_c, on steel pretreated with iron–phosphate coating were obtained, as compared to polyester coating on steel phosphated with accelerator, and on the bare steel. The surface roughness of phosphate coating deposited on steel from the bath without accelerator is favorable in forming stronger bonds with polyester coating. Namely, the dry and wet adhesion measurements are in accordance with EIS measurements in 3% NaCl solution, i.e. lower adhesion values were obtained for polyester coating on steel phosphated with accelerator and on the bare steel, while the iron–phosphate pretreatment from the novel bath enhanced the adhesion of polyester coating on steel.     

Novel isocyanate-free self-curable cathodically depositable epoxy coatings: Influence of epoxy groups on coating properties

Novel self-curable cathodically depositable coatings were developed from glycidyl functional epoxy ester-acrylic graft co-polymer (EEAG) without using any external crosslinking agents. The EEAG-amine adducts (EEAGAs) were prepared by reacting EEAG with varying amount of diethanolamine (DEoA) which are neutralized with acid and dispersed in deionised water to give stable dispersion for cathodic electrodeposition (CED) coatings. The dispersions were cathodically electrodeposited on phosphated steel panels and thermally cured to give uniform coating. The coatings were evaluated for different mechanical, chemical and corrosion resistance properties. The coatings were evaluated for their thermal properties using thermo gravimetric analysis (TGA). The final properties of the coatings were found to be affected by the amount of amine reacted with epoxy. The coating films showed good overall performance properties for their use in coating industry.     

Evaluation of the corrosion resistance of Ni-Co-B coatings in simulated PEMFC environment

The corrosion resistance behavior of Ni-Co-B coated carbon steel, Al 6061 alloy and 304 stainless steel was evaluated in simulated proton exchange membrane fuel cell (PEMFC) environment. The phase structure of the NiCoB based alloy was determined by Rietveld analysis. The PEMFC environment was constituted of 0.5 M H₂SO₄ at 60 °C and the evaluation techniques employed included potentiodynamic polarization, linear polarization resistance, open circuit potential measurements and electrochemical impedance spectroscopy. The results showed that in all cases the corrosion resistance of the Ni-Co-B coating was higher than that of the uncoated alloys; about two orders of magnitude with respect to carbon steel and an order of magnitude compared to 304 stainless steel. Except for the uncoated 304 type stainless steel, the polarization curves for the coated specimens did not exhibit a passive region but only anodic dissolution. The corrosion potential value, E_corr, was always nobler for the coated samples than for the uncoated specimens. This was true for the stainless steel in the passive region, but in the active state for the carbon steel and Al 6061 alloy. The corrosion of the underlying alloy occurred due to filtering of the solution through coating defects like microcracks, pinholes, etc. During the filtering process the E_corr value of the coating decreased slowly until it reached a steady state value, close to the E_corr value of the underlying alloy.     

Corrosion protection of AA2024-T3 using rare earth diphenyl phosphates

Existing corrosion protection technologies for aluminium alloys utilising chromates are environmentally damaging and extremely toxic. This paper presents a preliminary investigation into rare earth diphenyl phosphates as new environmentally benign corrosion inhibitors. Full immersion weight loss experiments, cyclic potentiodynamic polarisation measurements and Raman spectroscopy were used in this study. Results show cerium diphenyl phosphate (Ce(dpp)₃) acts as a cathodic inhibitor, decreasing cathodic current density and E_corr by passivating cathodic intermetallic particles on the alloy surface. Mischmetal diphenyl phosphate (Mm(dpp)₃) acts a mixed inhibitor, shifting E_corr to more noble values, decreasing cathodic current density, increasing the breakdown potential and suppressing pitting.     

Protective mechanisms occurring on zinc coated steel cut-edges in immersion conditions

Electrochemical processes occurring on the cut-edge of a galvanized steel immersed in NaCl solutions were studied using numerical simulations, and in situ current and pH profiles measured over the cut-edge. These results clearly demonstrate that only the steel surface remote from the zinc coating is cathodically active, oxygen reduction being strongly inhibited in the vicinity of zinc. This trend was confirmed by local polarization curves recorded on these distinct areas. Ex-situ AES and SEM analysis and cathodic polarization curves in solutions containing Zn²⁺ ions led to conclude that this cathodic inhibition was related to the fast nucleation of a dense Zn(OH)₂ film on the steel surface. After a long term exposure, a new galvanic coupling takes place between the Zn(OH)₂ covered area, showing an anodic activity, and the remaining steel surface covered by bulky white zinc corrosion products.     

Diphosphate coatings for protection of galvanized steel: quality control by impedance measurements

Galvanized steel surfaces can be protected against corrosion in natural waters by a superficial coating of zinc diphosphate, obtained by the partial oxidation of zinc in a solution containing diphosphate ions.Impedance measurements were used to study the improvement in corrosion protection resulting from this layer and to develop a quality control method. The mechanism of both anodic and cathodic processes remains the same in the presence of the coating as in its absence, so that the relationshipR _tI_corr=constant is valid (R _t is charge transfer resistance;I _corr is intensity of the corrosion current). Thereby, a protection factor, defined as the ratio of the corrosion currents in the absence and in the presence of the coating, can be estimated from the corresponding charge transfer resistances determined experimentally from impedance diagrams.Impedance data obtained on several test-pieces are in good agreement with the coating morphology, as shown by direct scanning electron microscope (SEM) observations, leading to a simple criterion for quality control.     

Electrochemical and structural evaluation of functionally graded bioglass-apatite composites electrophoretically deposited onto Ti6Al4V alloy

Titanium and its alloys are widely used as materials for implants, owing to their corrosion resistance, mechanical properties and excellent biocompatibility. However, clinical experience has shown that they are susceptible to localised corrosion in the human body causing the release of metal ions into the tissues surrounding the implants. Several incidences of clinical failures of such devices have demanded the application of biocompatible and corrosion resistant coatings and surface modification of the alloys. Coating metallic implants with bioactive materials is necessary to establish good interfacial bonds between the metal substrate and the bone. Hence, this work aimed at developing a bioglass-apatite (BG-HAP) graded coating on Ti6Al4V titanium alloy through electrophoretic deposition (EPD) technique. The coatings were characterized for their properties such as structural, electrochemical and mechanical stability. The electrochemical corrosion parameters such as corrosion potential (E_corr) (open circuit potential) and corrosion current density (I_corr) evaluated in simulated body fluid (SBF) have shown significant shifts towards noble direction for the graded bioglass-apatite coated specimens in comparison with uncoated Ti6Al4V alloy. Electrochemical impedance spectroscopic investigations revealed higher polarisation resistance and lower capacitance values for the coated specimens, evidencing the stable nature of the formed coatings. The results obtained in the present work demonstrate the suitability of the electrophoretic technique for the preparation of graded coating on Ti6Al4V substrates.     

Behaviour of molybdate-passivated zinc coated steel exposed to corrosive chloride environments

The behaviour of molybdate conversion coatings on zinc coated mild steel in corrosive chloride environments was investigated using electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS) and neutral salt fog exposure. It was found that the presence of a simple molybdate coating initially increased the rate of corrosion of zinc. Molybdenum species were initially present in the conversion coating in either the +V or +VI oxidation states. Exposure to neutral salt fog reduced molybdenum to either Mo(IV) or Mo(III). This reduction of molybdenum, an additional cathodic process, may result in the activation of zinc observed in these studies. For molybdate-passivated surfaces in the early stages of exposure to neutral salt fog, corrosion products were found to be less voluminous than those observed on untreated surfaces. This may be due to the presence of inhibiting Mo(IV) or Mo(III) species in the corrosion product layers. However, after 24 h exposure to salt fog, no molybdenum could be detected. This implies that the lower oxidation state molybdenum species formed are soluble. However, surfaces passivated from molybdate solutions appear to forestall the onset of red rust, during immersion in chloride solutions and exposure to salt fog, by approximately 12 to 24 h. This behaviour may be attributable to corrosion inhibition by Mo(III) and Mo(IV) species while they are present at the surface.     

Electropolymerization of poly(N-ethyl aniline) on mild steel: Synthesis, characterization and corrosion protection

Poly(N-ethylaniline) (PNEA) coatings on the mild steel electrode were synthesized by electrochemical oxidation of N-ethylaniline using aqueous oxalic acid solutions as reaction medium. Electrodeposition was carried out by potentiodynamic, potentiostatic and galvanostatic synthesis techniques. Smooth, adhesive and thick PNEA coatings on mild steel could be electrosynthesized during sequential scanning of the potential region between −0.5 and 1.4 V versus SCE, with scan rate of 20 mV s⁻¹. The electrodeposited coatings were characterized by cyclic voltammetry, FT-IR and UV-vis techniques. Corrosion behavior of PNEA coated steels was investigated by linear anodic potentiodynamic polarization technique and Tafel test. Anodic potentiodynamic polarization results showed that electrodissolution current value of PNEA coated steel decreased about 90% compared to that of the uncoated steel in 0.5 M H₂SO₄ aqueous solution. Tafel plots showed also strong decrease of corrosion current for the PNEA coated electrode compared to the uncoated steel electrode in 3% NaCl as corrosive medium.     

Electropolymerization of 2-Methoxyaniline: Kinetic Studies,Mechanism, Characterization of the Polymer and Applications as Corrosion Protection for Mild Steel in Acid Medium

Electropolymerization of 2-methoxyaniline on platinum electrode in acid medium was carried out under different reaction conditions as temperature, current density, hydrochloric acid, and monomer concentrations with reaction duration time. The initial rate of the electropolymerization reaction is small and the orders are found to be 1.18, 1.25, and 0.88 with respect to current density, HCl, and monomer concentrations, respectively. The apparent activation energy (Ea) is found to be 56.87 kJ/mol. The obtained polymer films are characterized by ¹H-NMR, elemental analysis, and IR spectroscopic studies. The mechanism of the electropolymerization reaction has also been discussed. The thermogravimetric analysis (TGA) was used to confirm the proposed structure and determination of the number of water molecules associated with each polymeric chain unit. X-ray and scanning electron microscopic analysis were used to investigate the surface morphology. The corrosion behavior of uncoated and coated mild steel electrode with poly (2-Methoxyaniline) in 1 M HCl at 25°C was investigated potentiodynamically. The various electrochemical parameters (I_corr, E_corr, and P%) were calculated from Tafel plots for uncoated and coated electrodes. The influence of some coating conditions as duration time, current density of the electropolymerization, and monomer concentrations were investigated. The data reveal that the presence of coated polymer films on the electrode surface increase the cathodic and anodic polarization compared to the uncoated sample.     

Selective area deposition of Tin–Nickel alloy coating – an alternative for decorative chromium plating

Sn–Ni alloy coatings on mild steel substrates produced by selective area deposition process with layer thickness of about 14 μm were investigated with regard to the structural and corrosion properties. X-ray diffraction analysis revealed that the selective area plated Sn–Ni alloy was heterogeneous and composed of NiSn, Ni₃Sn₂ and Ni₃Sn₄ phases. Uniform surface coverage of the substrate by granular morphology was observed from SEM and AFM. The alloy composition was determined by X-ray fluorescence (XRF). The corrosion protection performance of Sn–Ni alloy on mild steel was assessed using salt-water immersion and electrochemical corrosion tests. A sharp decrease in I _corr and high charge transfer resistance indicated improved corrosion resistant behavior of the selective area deposited Sn–Ni alloy.     

Corrosion Resistance of MgZn Alloy Covered by Chitosan-Based Coatings

Chitosan coatings are deposited on the surface of Mg20Zn magnesium alloy by means of the spin coating technique. Their structure was investigated using Fourier Transform Infrared Spectroscopy (FTIR) an X-ray photoelectron spectroscopy (XPS). The surface morphology of the magnesium alloy substrate and chitosan coatings was determined using Scanning Electron Microscope (FE-SEM) analysis. Corrosion tests (linear sweep voltamperometry and chronoamperometry) were performed on uncoated and coated magnesium alloy in the Hank’s solution. In both cases, the hydrogen evolution method was used to calculate the corrosion rate after 7-days immersion in the Hank’s solution at 37 °C. It was found that the corrosion rate is 3.2 mm/year and 1.2 mm/year for uncoated and coated substrates, respectively. High corrosion resistance of Mg20Zn alloy covered by multilayer coating (CaP coating + chitosan water glass) is caused by formation of CaSiO₃ and Ca₃(PO₄)₂ compounds on its surface.     

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.     

Deposition of zinc–zinc phosphate composite coatings on steel by cathodic electrochemical treatment

The present work aims at the development of an energy-efficient and eco-friendly approach for the deposition of zinc phosphate coatings on steel. The study describes the possibility of preparing zinc–zinc phosphate composite coatings by cathodic electrochemical treatment using dilute phosphoric acid as an electrolyte and zinc as an anode. The methodology enables the preparation of coatings with different proportions of zinc and zinc phosphate by suitably varying the applied current density, pH, and treatment time. Adhesion of the coating on mild steel and adhesion of paint film on the phosphate coating were found to be good. The surface morphology of the coatings exhibited platelet-type features and small white crystals (agglomerated at some places) which represented zinc and zinc phosphate, respectively. An increase in current density (from 20 to 50 mA/cm²) increased the size of the zinc crystals, and coatings prepared at 40 and 50 mA/cm² resembled that of electrodeposited zinc. Since the proportions of zinc and zinc phosphate could be varied with applied current density, pH, and treatment time, it would be possible to use this methodology to prepare coatings that would offer different degrees of corrosion protection.     

Polarization and impedance studies on zinc phosphate coating developed using galvanic coupling

Galvanic coupling technique is capable of producing coatings of desired thickness. Good quality coatings can be produced at low temperature. Galvanic coupling of mild steel (MS) with the other cathode materials such as titanium (Ti), copper (Cu), brass (BR), nickel (Ni), and stainless steel (SS) accelerates iron dissolution, enables quicker consumption of free phosphoric acid and facilitates an earlier attainment of point of incipient precipitation, resulting in a higher amount of coating formation. In the present investigation, potentiodynamic polarization and electrochemical impedance spectra on MS substrates phosphated using galvanic coupling are studied. This study reveals that MS substrates phosphated under galvanically coupled condition possess better corrosion resistance than the substrates phosphated under uncoupled condition.