Comparative study on corrosion protection properties of electroless Ni‐P‐ZrO2 and Ni‐P coatings on AZ91D magnesium alloy

Electroless Ni‐P‐ZrO₂ and Ni‐P coatings on AZ91D magnesium alloy were prepared, and their corrosion protection properties were compared in this paper. The potentiodynamic curves and electrochemical impedance spectroscopy (EIS) of the coated magnesium alloy in 3.5% NaCl solution showed that the corrosion performance of Ni‐P‐ZrO₂ composite coating was superior to that of Ni‐P coating. The same conclusion was obtained with salt spray and immersion tests. The corrosion morphologies of two kinds of coatings with various immersion time intervals in 3.5% NaCl solution indicated that most corrosion products concentrated on the nodules boundaries of Ni‐P coating and blocked corrosion pit was the main corrosion form. For the Ni‐P‐ZrO₂ coating, tortuous nodules boundaries were not the weak sites of the coating and corrosion initiated from the nickel phosphor alloy around the nanometer powders. Open corrosion pits occurred on the composite coating surface, and the coating was corroded gradually. Thus, the Ni‐P‐ZrO₂ coating exhibited better corrosion protection property to magnesium alloy substrate than Ni‐P coating.     

Synthesis and passivation behavior of electroless Ni–P‐CNT composite coating

Carbon nanotubes (CNTs) have high chemical stability, unique hollow nanotube structure, and are believed to be ideal materials for fabricating composites. In this study, Ni–P and Ni–P‐CNT composite coatings were fabricated by electroless plating. Scanning electron microscopy was used to characterize the coatings. The corrosion behavior of Ni–P and Ni–P‐CNT coated samples were evaluated by polarization curves and electrochemical impedance spectroscopy in 3.5 wt% NaCl and 0.1 M H₂SO₄ aqueous solutions at room temperature. The results indicated that incorporation of CNTs in the coating significantly increased corrosion resistance. The role of CNTs in improvement of corrosion resistance of the coating was also discussed.     

Electrochemical corrosion behavior of electroless Ni–P coating in NaCl and H2SO4 solutions

Electrochemical corrosion behavior of electroless Ni–P coating in NaCl and H₂SO₄ solutions were studied by potentiodynamic polarization curves and electrochemical impedance spectra techniques, as well as the corrosion morphology was characterized. The results indicate that electroless Ni–P coating with about 25 µm is stable in 30 days immersion in NaCl solution. Although it was corroded with prolonged immersion days, the corrosive medium has not penetrated through the coating. During the H₂SO₄ concentration ranging from 5 to 10%, the corrosion current density of electroless Ni–P coating increased due to the intensified anodic dissolution process; in 15% H₂SO₄ solution, electroless Ni–P coating shows obvious anodic passivation effect.     

Corrosion characteristics of electroless Ni–P coating in sulfur‐bearing solution

The corrosion behaviors of electroless Ni–P coatings deposited on carbon steel in sulfur‐bearing solutions were investigated by weight gain test and scanning electron microscopy. The results indicate that the corrosion rate of electroless Ni–P coating was directly related to the sulfur content, immersion time, and test temperature. The corrosion rate increased with the prolonged immersion time. Increasing the temperature can markedly increase the corrosion rate of electroless Ni–P coating. The electroless Ni–P coating had a better corrosion resistance than 316L stainless steel against Cl^? corrosion in sulfur‐bearing solution.     

Electrochemical corrosion behaviors and protective properties of Ni–Co–TiO2 composite coating prepared on sintered NdFeB magnet

In this paper, a protective Ni–Co–TiO₂ composite coating was prepared on the sintered NdFeB magnet by direct current electrodeposition. The surface morphologies, microstructure, and chemical composition of the composite coating were studied using scanning electron microscope (SEM), X‐ray diffraction (XRD), and energy dispersive spectroscopy (EDS), respectively. The surface morphologies and microstructure analysis showed that the composite coating possessed cauliflower‐like grain colonies, and formed face‐centered cubic (fcc) solid solution. The electrochemical corrosion behaviors of the composite coating in 0.5 mol/L H₂SO₄, 0.6 mol/L NaOH, 0.6 mol/L Na₂SO₄, and neutral 3.5 wt% NaCl solutions were evaluated by potentiodynamic polarization measurements and electrochemical impedance spectroscopy (EIS), showing good protection for NdFeB magnet. In order to further investigate the protective properties of the composite coating for NdFeB magnet and the practicability of the composite coating, the long‐term immersion test was carried out in neutral 3.5 wt% NaCl solutions using EIS. The results of long‐term corrosion test showed that the Ni–Co–TiO₂ composite coating could provide long‐term protection in neutral 3.5 wt% NaCl solutions for NdFeB magnet.     

The structure and properties of electroless Ni–Mo–Cr–P coatings on copper alloy

In the present study, the quaternary Ni–Mo–Cr–P alloy coatings were deposited on copper alloy by an electroless deposition process. Crystallization behavior and the effect of heat‐treatment on hardness and corrosion resistance of Ni–Mo–Cr–P deposits were detailedly investigated. X‐ray diffraction (XRD) analysis shows that as‐deposited Ni–Mo–Cr–P coatings are Ni–Mo–Cr–P solid solution and mixed crystal structure; the trend of microcrystallinity increases with the introduction of additional types of metal element; Ni–Mo–Cr–P alloy coatings start to occur in the crystallization with the heat‐treatment temperature increasing. With an increase in the annealing temperature, the hardness improves and reaches the maximum value at 500 °C. Further, it is found that Ni–Mo–Cr–P coatings have superior corrosion resistance than Ni–P and Ni–Mo–P deposits after the analysis of electrochemical measurements. Moreover, corrosion resistance increases before annealed at 400 °C, but heat‐treatment at higher temperatures has a negative effect on the corrosion resistance of Ni–Mo–Cr–P alloy coatings.     

Laser nanocrystallisation and corrosion behaviour of electroless Ni–W–P coating with high phosphorus content

This paper reports an investigation of microstructural characteristics in electroless Ni–3·9W–13·4P (wt.%) coating by laser nanocrystallisation using a quantitative X–ray diffraction (XRD) method and scanning electron microscopy (SEM) with energy dispersive X–ray spectroscopy (EDX). The corrosion resistance of the coatings before and after laser treatment has been evaluated in 0·5 M H₂SO₄ solution by potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) techniques. The results show that the laser treatment improves the corrosion resistance of the coatings. The corrosion mechanism has been studied and correlated to the microstructural characteristics including volume fraction of I_Ni3P/I_total, microstrain, and the crystallite size of the Ni and Ni₃P phases.     

Electrochemical behavior of nanocrystalline Ni–P alloys containing tin and tungsten

Autocatalytic ternary Ni-Sn-P, Ni-W-P and quaternary Ni-W-Sn-P films were prepared using an alkaline bath. Plain Ni-P films were also prepared for comparison. Corrosion resistance of the films was evaluated in 3.5% sodium chloride solution in non-deaerated condition by potentiodynamic polarization and electrochemical impedance spectroscopy methods. Deposits were also immersed in 3.5% sodium chloride solution for 7 days. All the coatings attained stable equilibrium potential within 30 minutes in NaCl medium. Lower corrosion current density values were obtained for ternary Ni-Sn-P coatings compared to the plain Ni-P coatings. Ternary Ni-W-P and quaternary Ni-W-Sn-P alloys did not show improved corrosion resistance compared to the ternary Ni-Sn-P coatings. Similar behavior of these coatings was further confirmed by the electrochemical impedance studies. After the potentiodynamic polarization test deposits were examined by scanning electron microscope. It was found that more corrosion occurred for the quaternary deposit compared to other deposits. Energy dispersive analysis of X-ray results indicated that more amount of Fe present on NiWP and NiWSnP coated samples. Similar behavior was confirmed from the optical images of the surfaces obtained for the deposits after the immersion test. The article is published in the original.     

Corrosion behavior of nanostructured Ni‐Si3N4 composite films: A study of electrochemical impedance spectroscopy

Ni‐Si₃N₄ nanocomposite films with both the consecutive Ni crystallites and dispersed Si₃N₄ particles in the nanometer range have been fabricated using DC electroplating technique, and characterized by scanning electron microscopy (SEM), transmission electron microscope (TEM), and X‐ray diffraction (XRD). The corrosion resistance of the Ni‐Si₃N₄ nanocomposite film has been compared to that of pure Ni coating through polarization. Meanwhile, the corrosion process of Ni‐Si₃N₄ nanocomposite film in neutral 3.5% NaCl solution has been investigated using electrochemical impedance spectroscopy (EIS). The results show that the Ni‐Si₃N₄ nanocomposite film is more resistant to corrosion than the pure Ni coating. The corrosion of Ni‐Si₃N₄ nanocomposite film is controlled by electrochemical step, and the whole corrosion process is divided into two sequential stages. The main corrosion type of Ni‐Si₃N₄ nanocomposite films in neutral 3.5% NaCl solution is pitting.     

Electroless deposited ternary alloys: third element chemical state,localisation and influence on the properties. A short review

Electroless deposited ternary alloys have been reviewed in relation to the chemical state of the third element, its localisation and the possible influence of these on alloy properties. Three types of electroless Ni–W–P, Co–W–P and Ni–Zn–P coatings have been investigated. Low P deposits are nanocrystalline and those with higher P content are amorphous. X-ray diffraction has proved the localisation of W, Zn and P along the nanograin boundaries. The localisation of Zn along with P has also been confirmed by transmission electron microscopy combined with energy dispersion spectroscopy. Analysing the X-ray photoelectron spectroscopy (XPS) spectra it has been found that within the coatings W is in elemental form, whereas Zn is partially oxidised. XPS data also show that the crystalline structure promotes the surface oxidation to a higher extent than in the case of amorphous structure. The wear resistance of nanocrystalline Ni–W–P coatings is much higher. A lower corrosion resistance of amorphous Ni–W–P coatings has been found by weight-loss method during long-term immersion in 5% NaCl. It is illustrated that in addition to the composition and structure, the properties depend on the distribution and chemical state of the alloy components.     

Effects of rare earth cerium addition on the synthesis and corrosion resistance of electroless Ni–PTFE–P coating

Electroless Ni–PTFE–P coatings have been successfully deposited on the surface of mild steel shaft from plating baths containing various concentrations of rare earth metal cerium (RE Ce). Surface morphology, Ce fraction, and thickness of the coatings were characterized by scanning electron microscope, inductively coupled plasma optical emission spectrometry, and reflection optical microscope, respectively. Salt spray test was used to determine the corrosion resistance of the coating. Results revealed that structure, compactness, and deposition rate of the Ni–PTFE–P coatings were increased significantly by addition of a small amount of RE Ce (10–20 ppm) to the plating bath. Electroless Ni–PTFE–P coating deposited from plating baths with 20 ppm Ce shows the highest corrosion resistance, owing to its high compactness and thickness. Deposition rate and corrosion resistance of the Ni–PTFE–P coating were deteriorated greatly as concentration of RE Ce in the plating baths exceeds 100 ppm.     

Structure and corrosion resistance of ZrO2 ceramic coatings on AZ91D Mg alloys by plasma electrolytic oxidation

The aim of this work is to study the structure and the corrosion resistance of the plasma electrolytic oxidation ZrO₂ ceramic coatings on Mg alloys. The ceramic coatings were prepared on AZ91D Mg alloy in Na₅P₃O₁₀ and K₂ZrF₆ solution by pulsed single-polar plasma electrolytic oxidation (PEO). The phase composition, morphology and element distribution in the coating were investigated by X-ray diffractometry, scanning electron microscopy and energy distribution spectroscopy, respectively. The results show that the coating thickness and surface roughness were increased with the increase of the reaction time. The ceramic coatings were of double-layer structure with the loose and porous outer layer and the compact inner layer. And the coating was composed of P, Zr, Mg and K, of which P and Zr were the main elements in the coating. P in the coating existed in the form of amorphous state, while Zr crystallized in the form of t-ZrO₂ and a little c-ZrO₂ in the coating. Electrochemical impedance spectra (EIS) and the polarizing curve tests of the coatings were measured through CHI604 electrochemical analyzer in 3.5% NaCl solution to evaluate the corrosion resistance. The polarization resistance obtained from the equivalent circuit of the EIS was consistent with the results of the polarizing curves tests.     

Investigation of hybrid PEO coatings on AZ31B magnesium alloy in alkaline K<Subscript>2</Subscript>ZrF<Subscript>6</Subscript>–Na<Subscript>2</Subscript>SiO<Subscript>3</Subscript> electrolyte solution

Detail study of the PEO coatings produced on AZ31B magnesium alloy in Na₂SiO₃–K₂ZrF₆-based electrolyte solution was carried out in this work. ZrO₂, MgF₂, MgO and Mg₂SiO₄ were observed as the major phases in the coatings. Electrolytic decomposition and then the severe thermochemical environment provoked various Zr–F–Mg based complexes in the coatings. From the surface analysis, various structures e.g, nano-grains, pores and volcano shape sintered material were evidenced. Using Vicker hardness test, maximum hardness was recorded as ~1280 HV. Potentiodynamic polarization technique in 3.5 wt % NaCl solution was used to predict the corrosion performances of the specimens. Among the coated samples, highest corrosion resistance was recorded to be ~223.5 × 10³ kΩ/cm² for 15 min coatings.     

Electrochemical corrosion behavior of plasma sprayed Al2O3‐13%TiO2 coatings in aqueous hydrochloric acid solution

One kind of conventional and two kinds of nanostructured Al₂O₃‐13%TiO₂ coatings were prepared by plasma spray process. The phase composition and microstructure of coatings were examined by means of scanning electron microscopy (SEM) and X‐ray diffraction (XRD). The potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) were used to investigate the corrosion behavior of coatings in aqueous hydrochloric acid solution. The results showed that nanostructured coatings had superior corrosion resistance compared to conventional Metco 130 coating. The corrosion resistance of coatings was mainly related to their microstructure and defects density. The EIS measurement for long time immersion in hydrochloric acid solution revealed that the corrosion resistance of coatings decreased with the increasing of immersion time. During the immersion period, electrochemical corrosion mainly occurred on the carbon steel substrate under NiCrAl coatings. In addition, the Al₂O₃‐13%TiO₂ coatings were also failed during corrosion in aqueous hydrochloric acid solution.     

A Comparative Study on the Effect of MWCNT as Reinforcement on the Corrosion Parameters of Different Ni–W/MWCNTs Nanocomposite Coatings in Various Corrosive Media

Nickel–tungsten multi-walled carbon nanotubes (Ni–W/MWCNTs) nanocomposite coatings were co-electrodeposited in the ammonium-free bath by means of constant direct current coulometry. The results indicate that the amount of MWCNTs incorporated into the nanocomposite coatings has a key role in the improvement of their microhardness and corrosion resistance. The corrosion behavior of the coatings was evaluated using potentiodynamic polarization and electrochemical impedance spectroscopy methods in three corrosive media of 3.5 wt% NaCl, 1.0 M NaOH, and 0.5 M H₂SO₄. The experimental data of the corrosion current density (j_corr), corrosion rate (CR), the polarization resistance (R_p), and microhardness indicate that the presence of MWCNTs in coatings improves the quality of those coatings. The surface morphology of the coatings and the elemental analysis data were obtained by scanning electron microscopy and energy dispersive X-ray microanalysis respectively. As the results showed, the coatings were uniform and crack-free in the presence of 5.3 wt% carbon. Also, a microhardness test revealed that the nanocomposite coating containing 5.3 wt% carbon obtained in an ammonium-free bath which provided the higher content of tungsten had the highest hardness value among others.     

Corrosion behaviour of Mg–Al alloys with Al–11Si thermal spray coatings

The corrosion resistance of AZ31, AZ80 and AZ91D Mg–Al alloys with Al–11Si thermal spray coatings was evaluated by electrochemical and gravimetric measurements in 3.5 wt% NaCl solution. The changes in the morphology and corrosion behaviour of the Al–11Si coatings induced by a cold‐pressing post‐treatment under 32 MPa were also examined. The as‐sprayed Al–11Si coatings revealed high degree of porosity and poor corrosion protection, which resulted in galvanic acceleration of the corrosion of the magnesium substrates. The application of a cold‐pressing post‐treatment produced more compact Al–11Si coatings with better bonding at the substrate/coating interface and slightly higher corrosion resistance. However, interconnected pores remained in the cold‐pressed coatings due to the low plasticity of the Al–11Si powder and galvanic corrosion of the substrate was observed after immersion in 3.5 wt% NaCl for 10 days.     

Microstructure and properties of open-cell Ni–Sn–P alloy foams prepared by electroless plating

In this study, open-cell Ni–Sn–P alloy foams were prepared by electroless plating. The influence of tin content on the surface morphology and properties of Ni–Sn–P alloy foams were investigated. The surface structure of Ni–Sn–P alloy foams became more uniform and compact with the increase of Sn content. The X-ray diffraction result showed that Ni–Sn–P alloy foams gradually transformed from an amorphous structure into crystallization with the increase of heat-treatment temperature. The introduction of Sn significantly enhanced the corrosion resistance of Ni–P coatings in 3.5 wt% NaCl solution, the corrosion current density decreased from 5.022 to 0.805 μA/cm² and the corrosion potential shifted positively from −0.423 to −0.294 V after adding 5.96 wt% Sn to Ni–P coatings. However, the corrosion resistance of Ni–Sn–P foams was deteriorated after heat treatment. Adding Sn to the Ni–P system slightly weakened the compressive strength of Ni–P binary foams. Nevertheless, significant improvement in the antioxidant performance of Ni–Sn–P alloy foams was indicated by the reduction of the mass change rate in that the mass change rate of Ni–P foams obviously reduced from 5.15% to 0.25% after adding 5.96 wt% Sn.     

Fabrication and anticorrosion performance of Ni–P–BN nanocomposite coatings on mild steel

Ni–P–BN composite coatings were successfully obtained on low carbon steel by the electroless plating technique. Deposits were characterized by the X-ray diffraction, scanning electron microscopy, and energy-dispersive analysis. The hardness and microstructure of as plated and heat treated Ni–P and Ni–P–BN composites were analyzed. Change in microstructure and higher hardness was noticed for the heattreated composite. The corrosion resistance of as plated and heat treated Ni–P and Ni–P–BN coatings was investigated by the Tafel plots and electrochemical impedance spectroscopy studies in 3.5 wt % NaCl. The heat-treated composite coatings exhibited enhanced corrosion resistance over that of Ni–P coatings.     

Erosion–corrosion characteristic of nano‐particulates reinforced Ni–Cr–Mo–Cu surface alloying layer in acidic flow and acidic slurry flow

In order to improve the corrosion and erosion–corrosion resistance of 316L stainless steel in engineering application, two kinds of composite alloying layers were prepared by a duplex treatment, consisting of Ni/nano‐SiC and Ni/nano‐SiO₂ predeposited by brush plating, respectively, and a subsequent surface alloying with Ni–Cr–Mo–Cu by double glow process. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) were performed on the two kinds of composite alloying layer using 10 wt% HCl solution to assess the corrosion behavior. Erosion–corrosion tests were carried out by erosion–corrosion test rig in acidic flow and acidic slurry flow for test time of 20 h at four different rotational speeds. Results of electrochemical tests indicated that the corrosion resistance of composite alloying layer with brush plating Ni/nano‐SiO₂ particles interlayer approximated to that of single Ni‐based alloying layer, whereas the corrosion resistance of the composite alloying layer with brush plating Ni/nano‐SiC particles interlayer was apparently inferior to that of Ni‐based alloying layer in 10 wt% HCl solution at static state. Under the conditions of acidic flow and acidic slurry flow, the mass losses of tested samples increased with increase in the time of erosion–corrosion tests and the rotational speeds of samples. The mass losses of composite alloying layer with brush plating Ni/nano‐SiO₂ particles interlayer were lower than that of single Ni‐based alloying layer at all rotational speeds, except at 1.88 m/s in acidic flow. The mass losses of composite alloying layer with brush plating Ni/nano‐SiC particles interlayer were higher than that of single Ni‐based alloying layer at all rotational speeds, but were obviously lower than that of AISI 316L stainless steel. The influences of second phase on the corrosion and erosion–corrosion of the two kinds of composite alloying layer were discussed in this paper.     

Improving the formation and protective properties of La-conversion coatings on brass by use of La2O3 nanoparticle incorporation with electrodeposition

The La₂O₃ nanoparticles incorporation and electrodeposition were used together to prepare the La-conversion coatings on brass surface in a basal solution containing rare earth salt and benzotriazole. The results showed that both of these techniques can improve the coatings formation and their protectiveness. A critical nanoparticulate La₂O₃ content and a critical deposition potential were observed, under which the conversion coatings had the highest protective properties. The composite La-conversion coatings could provide important protection against brass corrosion for considerable immersion periods in 3.5% NaCl solution because it ennobled the corrosion potential and decreased the anodic current.