Effect of sintering temperatures on corrosion and wear properties of sol-gel alumina coatings on surface pre-treated mild steel

Sol-gel alumina coatings were developed on the surface pre-treated (zinc-phosphated) mild steel substrate and subsequently sintered at 300 °C, 400 °C and 500 °C. The alumina sol was synthesised using aluminium iso-propoxide as a precursor material. FTIR of the boehmite (AlOOH) gel sintered at above-mentioned temperatures was employed to identify the presence of various functional groups. The microstructural features and the phase analysis of the sol-gel coated specimens were carried out using SEM and XRD respectively. The corrosion resistance of the sol-gel alumina coatings was evaluated by electrochemical measurement in 3.5% NaCl solution at room temperature. The abrasive wear behaviour of the sol-gel coated specimens was measured in two body (high stress) conditions. The experimental results revealed that the sol-gel coated specimen sintered at 400 °C has superior wear and corrosion resistance properties as compared to the sol-gel coated specimen sintered at 300 °C. However, the sol-gel coated specimen sintered at 500 °C has exhibited a very poor corrosion and wear resistance properties. Poor performance of the sol-gel coatings sintered at 500 °C could be explained to be due to (i) the presence of numerous cracks (ii) absence of organic groups in the coating.     

Scratch-resistant anticorrosion sol-gel coating for the protection of AZ31 magnesium alloy via a low temperature sol-gel route

A novel hybrid sol-gel/polyaniline coating has been developed for application onto an AZ31 magnesium alloy for corrosion protection. Electrochemical Impedance Spectroscopy in 3.5 wt% NaCl and diluted Harrison’s solutions, along with salt spray tests showed that the coating possesses excellent corrosion resistance. The hybrid coating was modified by doping with silica nanoparticles (for scratch resistance) and cured at a low temperature of 75 °C. Whilst conventional sol-gel methods tend to limit the coating thickness values up to 10 μm, the new hybrid sol-gel/polyaniline system presented here allows thick coatings to be deposited, in this case, around 50-60 μm.     

The corrosion performance of anodised magnesium alloys

The corrosion performance of anodised magnesium and its alloys, such as commercial purity magnesium (CP-Mg) and high-purity magnesium (HP-Mg) ingots, magnesium alloy ingots of MEZ, ZE41, AM60 and AZ91D and diecast AM60 (AM60-DC) and AZ91D (AZ91D-DC) plates, was evaluated by salt spray and salt immersion testing. The corrosion resistance was in the sequential order: AZ91D ≈ AM60 ≈ MEZ ? AZ91D-DC ? AM60-DC > HP-Mg > ZE41 > CP-Mg. It was concluded the corrosion resistance of an anodised magnesium alloy was determined by the corrosion performance of the substrate alloy due to the porous coating formed on the substrate alloy acting as a simple corrosion barrier.     

Vanadia-based coatings of self-repairing functionality for advanced magnesium Elektron ZE41 Mg–Zn–rare earth alloy

A smart vanadia protective coating of self-repairing functionality that has proven to provide superior corrosion resistance for several magnesium and aluminum alloys has successfully been designed by our group. A newly developed series of magnesium alloys, namely ZE41 alloy, has recently been proposed for automotive, electronics and aerospace applications. The advanced ZE41 alloy possesses very low density, high specific strength, and good castability and weldability characteristics compared to aluminum and steel based alloys. However, the corrosion resistance of ZE41 alloy in the presence of corrosive chloride environment is relatively low. The possibility of utilizing such coatings to add self-repairing functionalities to ZE41 alloy was discussed in this paper. The electrochemical corrosion behavior of the vanadia coatings over ZE41 alloy was investigated in 3.5% NaCl solution using EIS, linear polarization and cyclic voltammetry techniques. The optimum conditions for obtaining protective vanadia coatings of self-repairing abilities and improved localized corrosion resistance were determined. Surface examination of the coatings was investigated using SEM-EDS and macroscopic imaging.     

Preparation of MgO coatings on magnesium alloys for corrosion protection

MgO coating is formed on magnesium alloy by anodic electrodeposition in 6 M KOH solution, whereas Mg(OH)₂ coating is produced by anodization in 10 M KOH solution, which could be successively converted to MgO by calcination in air at 450 °C. The evolution of morphology, structure and composition of anodic film obtained on Mg alloy is investigated using scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDX) and X-ray diffraction (XRD). Potentiodynamic polarization measurements show that the as-grown MgO protective coatings are very effective in improving the corrosion resistance of magnesium alloy compared to bare metallic magnesium.     

Corrosion behaviour of thermally sprayed Al and Al/SiCp composite coatings on ZE41 magnesium alloy in chloride medium

Thermally sprayed Al and Al/SiCp composite coatings have been deposited on ZE41 magnesium alloy and mechanical compaction at room temperature was applied to the Al and Al/SiCp coatings to reduce their porosity. Corrosion behaviour of coated samples was evaluated and compared to that of uncoated substrate in 3.5 wt.% NaCl solution using electrochemical measurements. Al and Al/SiCp composite coatings reduced the corrosion current density of Mg-Zn alloys by three and two orders of magnitude, respectively, and reductions up to four orders of magnitude were obtained after mechanical compaction.     

Plasma anodized ZE41 magnesium alloy sealed with hybrid epoxy-silane coating

Anodic coatings on magnesium ZE41 alloy were formed by DC plasma electrolytic oxidation (PEO) in spark regime in solution composed of NaOH, Na₂SiO₃ and KF. The positive effect of poly(ethylene oxide) addition into the anodizing electrolyte on PEO process, anodic film porosity and its protective performance was described. Anodic films were sealed with hybrid epoxy-silane formulation. The corrosion behavior of the coated ZE41 was studied through electrochemical impedance spectroscopy (EIS) in 0.6 M NaCl solution. Resulting duplex PEO/epoxy-silane coating provides good protective performance without significant signs of corrosion during 1 month of immersion test.     

A study on the electroless Ni-P deposition on WE43 magnesium alloy

In this paper an attempt has been made to understand the mechanism of the deposition process of an electroless Ni-P (EN) coating on WE43 magnesium alloy. Also a number of properties concerning the deposited coatings have been reviewed. The results show that the starting microstructure of the alloy consists of a primary α phase together with some eutectic β phase at triple points and along with some grain boundaries. Microstructural studies reveal an uneven distribution of alloying elements in the phases and they are predominantly segregated to the eutectic β phase. This phenomenon can result in galvanic coupling between eutectic β and primary α phases. Detailed studies prove that the replacement reaction takes place at the early stages of coating, and is followed by the autocatalytic reaction at the next stages of deposition.The X-ray diffraction patterns of primitive coatings show a broad peak around 2θ of 45°, which is an indication of an amorphous or an extremely fine crystalline structure. Annealing at 400 °C for an hour led the nature of deposits to be changed to crystalline phases of Ni, Ni₃P, and NiP₃. Microhardness values of coatings are considerably higher than those of the bare substrate. These further increase when they are annealed at 400 °C for 1 h. Electrochemical polarization curves and calculated corrosion values reveal higher corrosion potential (E_corr) for the coating than for the bare substrate. This decreases again when the coating is annealed at 400 °C for 1 h.     

Effect of plasma surface treatment on mechanical and corrosion protection properties of UV-curable sol-gel based GPTS-ZrO2 coatings on mild steel

Hybrid sol-gel based nanocomposite coatings derived from hydrolysis and condensation of a photopolymerizable silane precursor 3-Glycidoxypropyltrimethoxy silane in combination with zirconium-n-propoxide were deposited on mild steel substrates by a dip coating technique. In some cases, substrates were subjected to an atmospheric air-plasma surface pre-treatment prior to coating deposition. The coatings were subsequently densified by exposure to ultraviolet radiation followed by a thermal treatment at 250 °C. Characterization of the coatings with respect to thickness, water contact angle, pencil scratch hardness, adhesion and abrasion resistance was carried out. Corrosion testing was carried out on the coatings for a 1 h exposure to a 3.5% NaCl solution by electrochemical polarization and impedance measurements. The hybrid sol-gel coatings were found to improve the mechanical properties and corrosion resistance of mild steel. Plasma surface pre-treatment was found to improve the adhesion of coatings significantly and decreased the corrosion rate from 0.2652 mpy obtained for coatings without any surface pre-treatment to 0.0015 mpy, which was nearly 600 times lower than that of bare mild steel.     

Ceria/stannate multilayer coatings on AZ91D Mg alloy

In this work, CeO₂/stannate multilayer coatings on AZ91D magnesium alloy were successfully obtained by chemical conversion and sol–gel dip coating. The stannate conversion coatings were prepared from a stannate aqueous bath containing Na₂SnO₃, CH₃COONa, Na₃PO₄ and NaOH at different temperatures and immersion times. Ceria films were produced on stannate/AZ91D starting from Ce(III) nitrate solutions in H₂O. In some cases, the PVA was added as chelating agent. Ceria top coatings were fired at 200 °C for 1 h. Coating microstructure was examined by FE-SEM. Finally, the corrosion resistance features of the coatings were tested by the electrochemical impedance spectroscopy (EIS) in 3 wt.% NaCl solution. The effect of PVA addition was evaluated in terms of microstructure and corrosion resistance features. CeO₂/stannate multilayer films, 3 μm thick, uniform, well adherent and nearly crack free were obtained. The formation of CeO₂ phase was confirmed by XRD and XPS analyses. The XPS depth profiles showed a limited diffusion of Mg towards the ceramic film. The EIS tests showed a significant improvement of corrosion resistance of the multilayer coatings (~ 16.6 kΩ after 48 h in NaCl solution) with respect to the blank alloy (~ 2.4 kΩ after 48 h in NaCl solution).     

Cold Spray Al-5% Mg Coatings for the Corrosion Protection of Magnesium Alloys

Poor corrosion resistance is a significant limitation of magnesium alloys as structural materials. To address this problem, the objective of this study was to apply to a magnesium alloy a corrosion-resistant barrier coating that has galvanic compatibility with magnesium and a hardness value no less than that of magnesium. Aluminum coatings were applied to ZE41A-T5 Mg by the cold spray process. A custom-made high-purity Al-5 wt.% Mg powder was produced by spray metal forming for the coating evaluation. In addition, coatings of commercially pure Al (99.5 wt.%), high-purity Al (99.95 wt.%), AA5356, and AA4047 were used for comparison. Coating evaluation included mechanical testing (hardness and adhesion strength) and corrosion testing (salt spray, galvanic coupling, and crevice corrosion). The Al-5% Mg powder resulted in the best overall performance, including a high hardness, 125 H_v100, and an adhesion strength, over 60 MPa, when treated for over 1000 h in a salt spray chamber and with a low galvanic current.     

Deposition, characterization and performance evaluation of ceramic coatings on metallic substrates for supercritical water-cooled reactors

A series of ceramic coatings have been prepared on P91 substrates by spray pyrolysis processes and on Zr-2.5Nb substrates by a plasma electrolytic oxidation process. Preliminary results show that coatings obtained with different solution compositions and procedures can reduce the oxidation weight gain of P91 samples by factors of 2-10 for exposure times up to 500 h in deaerated supercritical water at 500 °C and 25 MPa. Results also show that the weight gain of a P91 sample with an alumina (Al₂O₃) coating is about nine times less than that of uncoated P91 after exposures for 400 h in deaerated supercritical water at 650 °C and 25 MPa. These results indicate that the Al₂O₃ coating shows promising results for preventing oxidation of P91 under supercritical water conditions. The samples with ceramic coatings on Zr-2.5Nb substrates show marginally improved corrosion resistance compared to the bare substrates.     

Evaluation of the anti-corrosive effect of acid pickling and sol-gel coating on magnesium AZ31 alloy

The effect of different acid pre-treatment procedures on the corrosion of magnesium AZ31 alloy was compared by measuring the amount of hydrogen gas formed when the surface was in contact with aqueous 5% sodium chloride solution. A 4-7 μm thick sol-gel coating prepared by phosphoric acid catalyzed sol-gel processing of a methyltriethoxysilane/tetraethoxysilane mixture was applied to the differently pre-treated magnesium surfaces. The corrosion rate of the alloy decreased by a factor of up to 60 by combination of acid pickling and sol-gel coating. The addition of triethylphosphate or 1,2,4-triazole as corrosion inhibitors led to further improvements. Composition and texture of the films was investigated by scanning electron microscopy and energy dispersive X-ray analysis.     

Influence of thermal exposure on the stability of metastable microstructures of sputter deposited nanocrystalline 304 and 310 stainless steel coatings

The effect of thermal exposure on the stability of the microstructures of magnetron sputter deposited 304 and 310 stainless steel (SS) coatings have been investigated. The coated 304SS samples were exposed to thermal cycling between 750 °C and room temperature and aged at 500 °C and 650 °C. X-ray diffraction (XRD) results revealed that the microstructures of the as-deposited 304SS and 310SS coatings consisted of αFe + σ and γFe + αFe, respectively. Thermal exposure at 500 °C and 650 °C resulted in the dissolution of σ and partial transformation of αFe into γFe in the 304SS coating and led to the precipitation of σ phase particles, at the expense of αFe, in the 310SS coating. The amount of σ phase in the 310SS coating increased with exposure time. However, both coatings showed no σ phase after thermal cycling to 750 °C for approximately 500 cycles.     

Investigation of Plasma Electrolytic Oxidation (PEO) coatings on a Zr-2.5Nb alloy using high temperature/pressure autoclave and tribological tests

A Plasma Electrolytic Oxidation (PEO) process was used to produce thin oxide coatings on a Zr-2.5 wt% Nb alloy. Effects of current density on surface morphologies and wear properties of PEO coatings were investigated and compared to the uncoated substrate and a commercially used black oxide coating. Corrosion properties at ambient and high temperature/pressure conditions were studied using potentiodynamic polarization tests and autoclave tests, respectively. Up to 30-day autoclave experiments were carried out in an aqueous condition of 300 °C and 10 MPa in 0.05 M LiOH solutions. It was found that most of the micro-pores which were produced during the PEO treatment were closed after the autoclave experiments. PEO coatings had larger weight gains in the first 10 exposure days than the black oxide coating. However, after 10 days, the corrosion rate of black oxide coating accelerated and exhibited a similar weight gain to PEO coatings after 30 days. PEO coatings prepared at low current densities had lower weight gains. Although the black oxide coating exhibited a good corrosion resistance, it had a much lower wear resistance than the PEO coatings. Compared with the uncoated substrate, all PEO coatings had a higher corrosion resistance, lower weight gain during autoclave tests and better wear resistance.     

Nanoscratching deformation and fracture toughness of electroless Ni-P coatings

In the present investigation electroless Ni-P coatings were prepared. Structural characterizations indicated that the as-deposited coating had an amorphous structure with a P content of 23 at.%. The deformation behavior of an electrolessly amorphous Ni-P coating was investigated by using the Vickers indentation and the Tribo-indenter instrumented nano-indentation technique. The hardness of the Ni-P coating is remarkably improved after proper heat-treatment and the hardness is as high as 12.7 GPa for the coating annealed at 400 °C for 1 h. However, the cracks were observed during the indentation of the Ni-P coatings annealed at 400 °C and 500 °C for 1 h. The corresponding fracture toughness was evaluated as 2.58 MPa m^0.5 and 1.33 MPa m^0.5, respectively. Nanoscratching tests indicated that the wear resistance of the Ni-P coatings was improved significantly with an increasing ratio of hardness (H) to elastic modulus (E). It was observed that the friction coefficient increased from 0.083 ± 0.006 for the Ni-P coating annealed at 300 °C up to 1.337 ± 0.009 for the IF steel substrate, while the H/E simultaneously decreased from 0.084 (10.7/128) to 0.009 (1.85/200). The study revealed that the electrolessly amorphous Ni-P coating had offered better corrosion resistance than the Ni-P coatings after heat-treatment. An annealing temperature of 300 °C is preferentially suggested for the trade-off between the wear resistance property and anti-corrosion property of the Ni-P coating.     

Annealing temperature effect on the corrosion parameters of autocatalytically produced Ni-P and Ni-P-Al2O3 coatings in artificial seawater

Ni-P and Ni-P-Al₂O₃ amorphous alloy coatings with 9.3 and 8.3 wt.% P respectively were obtained by autocatalytic deposition at 90 °C on carbon steel substrates. The effect of annealing temperature (100, 200, 300, 400 and 500 °C) upon the corrosion parameters of the coatings in artificial seawater with pH 5.0 and 8.1 at room temperature was evaluated by potentiodynamic polarisation and electrochemical impedance spectroscopy. It was found that deposits annealed at 400 and 500 °C presented an increase of the charge transfer resistance and negligible changes on samples annealed at lower temperature. Polarisation tests showed a charge transfer controlled anodic kinetics on both Ni-P and Ni-P-Al₂O₃ deposits and diffusion controlled cathodic reaction in artificial seawater at pH 5.0 and 8.1. The coatings did not present passive behaviour in the electrolytes and impedance measurements showed a single time constant for all cases with the lowest double layer capacitance (C_dl) for samples annealed at 400 and 500 °C. The best corrosion parameters were observed on Ni-P and Ni-P-Al₂O₃ coatings annealed at temperatures higher than 400 °C, which is the temperature where crystallisation of this kind of coatings takes place.     

Enhancement of resistance to galvanic corrosion of ZE41 Mg alloy by equal channel angular pressing

The galvanic corrosion behavior of as-received and ECAPed ZE41 Mg alloy coupled with Al7075 alloy is investigated using zero resistance ammeter in three different corrosive environments, 0, 0.1, and 1 M NaCl, to mimic the conditions experienced in engineering applications. The mechanism of galvanic corrosion for the ZE41 Mg–Al7075 aluminum alloy is explained. It is observed that a robust surface film containing a composite layer of oxide/hydroxide of magnesium and aluminum is established in deionized water (0 M). However, only a single layer of magnesium oxide/hydroxide is detected in chloride-containing environments. Equal channel angular pressing (ECAP) improved the resistance to galvanic corrosion by 58% and 54% when compared with the as-cast counterparts in 0 and 1 M NaCl solution, respectively. In contrast, galvanic corrosion resistance decreased by 26% in 0.1 M NaCl after ECAP while the as-received samples evinced pits unfavorable to be used in engineering applications. ECAP is a promising method to combat galvanic corrosion encountered by ZE41 magnesium alloy used in automobiles and components of military vehicles.     

Influence of pH on the deterioration of plasma electrolytic oxidation coated AM50 magnesium alloy in NaCl solutions

The corrosion deterioration process of plasma electrolytic oxidation (PEO) coatings on AM50 magnesium alloy prepared from two different based electrolytes, i.e., an alkaline phosphate electrolyte and an acidic fluozirconate electrolyte, were investigated using electrochemical impedance spectroscopy (EIS) in a 0.1 M NaCl solution with pH of 3, 7 and 11, respectively. It was found that the PEO coating formed in alkaline phosphate electrolyte, which was composed mainly of MgO, suffered from rapid chemical dissolution and lost its protection capability very quickly in acidic NaCl solution (pH 3). The chemical dissolution of this PEO coating was retarded in neutral NaCl solution (pH 7) and the corrosion damage was localized in this environment. On the other hand, in the alkaline NaCl solution (pH 11), the MgO coating underwent only slight degradation. The PEO coating produced in acidic fluozirconate electrolyte, the failure was marked by the flaking-off of the large areas of coating in acidic NaCl solution (pH 3). However, in the neutral and alkaline NaCl solutions, the coating underwent only a slight degradation without any observable corrosion damage in the 50 h test. The results showed that the deterioration process of PEO coated magnesium alloy was governed mostly by the pH of NaCl solution and it was also strongly related to the microstructure and composition of the PEO coatings.     

Influence of sodium silicate concentration on properties of micro arc oxidation coatings formed on AZ91HP magnesium alloys

In a base solution containing 10 g/L sodium hydroxide and 12 g/L phytic acid, the influence of sodium silicate concentration on the formation and properties of anodic coatings obtained by micro arc oxidation (MAO) on magnesium alloys was systematically studied. The results demonstrate that sodium silicate can increase the solution conductivity, decrease the final voltage and change the coating color. Amorphous magnesium silicate is detected and the silicon content in the coatings continually increases with the increasing of sodium silicate concentration. Silicate ions can simultaneously combine with magnesium and aluminum ions to develop anodic coatings, while phytic acid radicals preferentially react with magnesium ions. Sodium silicate can further improve the corrosion resistance of MAO treated magnesium and the coating shows the best corrosion resistance in the base solution with 10 g/L sodium silicate.