Electrochemical impedance spectroscopy (EIS) study of nano-alumina modified alkyd based waterborne coatings

A nano-composite coating was formed by dispersing nano-Al₂O₃ as pigments in different concentrations, to a specially developed alkyd based waterborne coating. The nano-Al₂O₃ based composite coatings were applied on mild steel substrate by dipping. The dispersion of particles in coating system was investigated by using SEM and AFM techniques. The effect of addition of these nano-pigments on the electrochemical behavior of the coating was investigated in 3.5% NaCl solution, using electrochemical impedance spectroscopy (EIS). It was found that coating modified with higher concentration of nano-Al₂O₃ particles showed comparatively better performance as it was evident from pore resistance (R_p) and coating capacitance (C_c) values after 30 days of exposure. In general, the study showed an improvement in the corrosion resistance of the nano-particle modified coatings as compared to the neat coating, confirming the positive effect of nano-particle addition in coatings.     

Studying the influence of nano-Al2O3 particles on the corrosion performance and hydrolytic degradation resistance of an epoxy/polyamide coating on AA-1050

The aim of this work was studying the effects of addition of Al₂O₃ nanoparticles on the anticorrosion performance of an epoxy/polyamide coating applied on the AA-1050 metal substrate. For this purpose, the epoxy nanocomposites were prepared using 1, 2.5 and 3.5 (w/w) pre-dispersed surface modified Al₂O₃ nanoparticles. Field-emission electron microscope (FE-SEM) and ultraviolet–visible (UV–Vis) techniques were utilized in order to evaluate the nanoparticles dispersion in the epoxy coating matrix. The anticorrosion performance of the nanocomposites was studied by electrochemical impedance spectroscopy (EIS) (in 3.5 wt% NaCl solution for 135 days immersion) and salt spray test for 1000 h. The coating resistance against hydrolytic degradation was also studied by optical microscope and Fourier-transform infrared spectroscopy (FTIR). Results obtained from FE-SEM micrographs and UV–visible spectra showed that the nanoparticles dispersed in the coating matrix uniformly with particle size less than 100 nm even at high loadings. Results revealed that nano-Al₂O₃ particles could significantly improve the corrosion resistance of the epoxy coating. Nanoparticles reduced water permeability of the coating and improved its resistance against hydrolytic degradation.     

Composite Ni/Al2O3 coatings and their corrosion resistance

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

Retention of Mechanical and Thermal Properties of Hydrothermal Aged Glass Fiber-Reinforced Polymer Nanocomposites

The combined effect of nano-Al₂O₃ and TiO₂ fillers on residual mechanical and thermal properties of glass fiber-reinforced polymer composites has been evaluated. The results reveal that the addition of 0.1?wt% of Al₂O₃ and 0.1?wt% of TiO₂ into the epoxy matrix reduces the water diffusivity by 12%. The residual flexural and interlaminar shear strength of the nanocomposite have been increased by 19 and 21%, respectively, as compared to those of neat epoxy glass fiber-reinforced polymer composite. In spite of reduction in water diffusivity and increase in strength, there was no improvement in glass transition temperature of the nanocomposites.     

Electrolytic deposition of Ni-Co-Al2O3 composite coating on pipe steel for corrosion/erosion resistance in oil sand slurry

To improve the resistance of the hydrotransport pipe steel to corrosion and erosion in oil sand slurry, a Ni-Co-Al₂O₃ composite coating was fabricated by electrolytic deposition on X-65 pipe steel substrate. Potentiodynamic polarization curve and electrochemical impedance measurements show that the deposited coating significantly improves the corrosion resistance of the steel in water-oil-sand solution that simulates the chemistry of oil sand slurry. The corrosion resistance of the coating increases with the increasing Al₂O₃ particle concentration in electrolyte, cathodic current density, electrode rotating speed and temperature. However, a maximum value of corrosion resistance as a function of the depositing parameters is observed, indicating that the optimal electrodepositing parameters and operating conditions are essential to the maximization of the corrosion resistance of the coated steel in oil sand slurry. The optimal depositing conditions are suggested in the given system. The morphology, structure and composition of the coatings were characterized by scanning electron microscopy and energy-dispersive X-ray analysis. The Ni-Co-Al₂O₃ composite coating develops a compact, uniform, nodular structure with an average thickness of 50-200 microns. The Al₂O₃ amount in the coating increases with the increasing Al₂O₃ concentration in electrolyte, which also enhances the co-deposition of Ni and Co. The micro-hardness and wear resistance of the composite coatings are much higher than the steel substrate and increase with the increasing Al₂O₃ particle amount in the coating.     

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.     

Synergistic effect of CeO2 and Al2O3 nanoparticle dispersion on the oxidation behavior of MCrAlY coatings deposited by HVOF

In this study, the as-received and nano-scaled oxide dispersion strengthened (ODS) MCrAlY coatings were deposited using high-velocity oxy-fuel (HVOF) spraying process. The high-energy planetary ball-milling process was utilized to prepare CeO₂ and Al₂O₃ nanoparticles. ODS-NiCoCrAlY feedstock powders were also developed using the ball-milling process. The various formulations of Al₂O₃ and CeO₂ nanoparticles (0.5 and 1.0 wt%) were chosen to apply different types of ODS-NiCoCrAlY coatings. The microstructure of the as-received and ODS coatings were evaluated by field emission scanning electron microscope (FESEM) as well as the commercial and ODS powders. Furthermore, the microhardness of different compositions of ODS coatings was accordingly investigated and the obtained results were compared with as-received coating. On account of the measurement of oxidation kinetics, the freestanding as-received and ODS coatings were exposed to air at 1000 °C up to 500 h and the thickness growth rate of the α-Al₂O₃ oxide layer was simultaneously examined. The results exemplified that NiCoCrAlY+1.0 wt% nano-CeO₂+0.5 wt% nano-Al₂O₃ coating had a better oxidation resistance and lower oxide scale growth rate under the synergistic effects of both CeO₂ and Al₂O₃ nanoparticles.     

Application of EIS and salt spray tests for investigation of the anticorrosion properties of polyurethane-based nanocomposites containing Cr2O3 nanoparticles modified with 3-amino propyl trimethoxy silane

The Cr₂O₃ nanoparticles were modified with 3-amino propyl trimethoxy silane in order to obtain proper dispersion and increment compatibility with the polyurethane coating matrix. The nanocomposites prepared were applied on the St-37 steel substrates. The existence of 3-amino propyl trimethoxy silane on the surface of the nanoparticles was investigated by Fourier transform infrared (FTIR) spectroscopy and thermal gravimetric analysis (TGA). Dispersion of the surface modified particles in the polyurethane coating matrix was studied by a field emission-scanning electron microscope (FE-SEM). The electrochemical impedance spectroscopy (EIS) and salt spray tests were employed in order to evaluate the corrosion resistance of the polyurethane coatings. Polarization test was done in order to investigate the corrosion inhibition properties of the Cr₂O₃ nanoparticle on the steel surface in 3.5 wt.% NaCl solution. The adhesion strengths of the coatings were evaluated by pull-off adhesion tester before and after 120 days immersion in 3.5 wt.% NaCl solution. FT-IR and TGA analyses revealed that surface modification of the nanoparticles with 0.43 silane/5 g pigment resulted in the greatest amount of silane grafting on the surface of particles. Results obtained from FE-SEM analysis showed that the surface modified nanoparticles dispersed in the coating matrix properly. Results obtained from EIS and salt spray analyses revealed that the surface modified particles enhanced the corrosion protection performance of the polyurethane coating considerably. The improvement was more pronounced for the coating reinforced with 0.43 g silane/5 g pigment. Moreover, the adhesion loss decreased in the presence of surface modified nanoparticles with 0.43 silane/5 g pigment.     

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

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

Preparation of Al2O3 coating on TiN coating by polymer-assisted deposition to improve oxidation resistance in coking inhibition applications

In order to inhibit the metal catalytic coking and improve oxidation resistance of single TiN coating, the TiN/Al₂O₃ double layer coatings were designed as a chemically inert coating for methylcyclohexane supercritical pyrolysis. Internal TiN coatings were prepared by atmospheric pressure chemical vapor deposition using TiCl₄–H₂–N₂ system. The external Al₂O₃ coatings with different thicknesses were prepared on the TiN surface by polymer-assisted deposition, and the coating with the most suitable thickness was further annealed at different temperatures of 600, 700, 800 and 900 °C. The morphology, elemental and phase composition of TiN/Al₂O₃ coatings were characterized by SEM, EDX and XRD respectively. The chemical state information of the coating elements was based on Ti 2p, Al 2p core level X-ray photoelectron spectroscopy (XPS) spectra. The results indicated that the external Al₂O₃ coating will partially peel off at 900 °C annealing temperature. The thermogravimetric analysis results indicated that all TiN/Al₂O₃ coatings show better oxidation resistance than single-layer TiN coating. The anti-coking test with methylcyclohexane supercritical pyrolysis showed that the TiN/Al₂O₃ coatings can effectively cover the metal catalytic sites and eliminate metal catalytic coking. However, the acid sites of external Al₂O₃ coating slightly promoted coking, so the anti-coking ratios of TiN/Al₂O₃ coatings were smaller than that of TiN. Thus, the addition of external Al₂O₃ coating can greatly improve the oxidation resistance of TiN coatings with little loss of coking resistance.     

Thermal shock resistance and mechanical properties of La2Ce2O7 thermal barrier coatings with segmented structure

La₂Ce₂O₇ (LCO) is a promising candidate material for thermal barrier coatings (TBCs) application because of its higher temperature capability and better thermal insulation property relative to yttria stabilized zirconia (YSZ). In this work, La₂Ce₂O₇ TBC with segmentation crack structure was produced by atmospheric plasma spray (APS). The mechanical properties of the sprayed coatings at room temperature including microhardness, Young's modulus, fracture toughness and tensile strength were evaluated. The Young's modulus and microhardness of the segmented coating were measured to be about 25 and 5 GPa, relatively higher than those of the non-segmented coating, respectively. The fracture toughness of the LCO coating is in a range of 1.3–1.5 MPa m^1/2, about 40% lower than that of the YSZ coating. The segmented TBC had a lifetime of more than 700 cycles, improving the lifetime by nearly two times as compared to the non-segmented TBC. The failure of the segmented coating occurred by chipping spallation and delamination cracking within the coating.     

Tribological properties of selected ceramic coatings

The paper presents the characteristics of some ceramic coatings obtained by a plasma spray method. The ceramic coatings Al₂O₃, Cr₂O₃ and Cr₂O₃?+?5% TiO₂ were evaluated. Also the influence of the NiCr interlayer on the functional properties of sprayed coatings was studied. Other parameters studied included: thickness; microhardness; adhesion of the coatings; resistance to abrasive wear and thermal cyclic loading. The addition of TiO₂ to the Cr₂O₃ material increased the coating density, but did not substantially reduce the hardness. On the other hand, the lowest loss of material thickness was seen for Cr₂O₃; while the Al₂O₃ and the Cr₂O₃?+?5 wt.% TiO₂ material showed a higher loss. The loss in the case of the latter two was about the same. Relatively, higher values of abrasive wear resistance were observed in the Cr₂O₃ coatings, as compared to the reference material (Al₂O₃ coating), and the highest microhardness values were measured in the Cr₂O₃ coating. Finally, the metal interlayers in all coatings increased their resistance to thermal shock. All the coatings, using the interlayer to reduce differences in coefficients of thermal expansion, were suitable for the purpose of the thermal loading up to 1000?°C.     

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

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

Synthesis and electrochemical characteristics of Al2O3-coated LiNi1/3Co1/3Mn1/3O2 cathode materials for lithium ion batteries

LiNi_1/3Co_1/3Mn_1/3O₂ cathode materials have been coated with Al₂O₃ nano-particles using sol-gel processing to improve its electrochemical properties. The X-ray diffraction (XRD) pattern of the as-prepared Al₂O₃ nano-particles was indexed to the cubic structure of the γ-Al₂O₃ phase and had an average size of ∼4 nm. The XRD showed that the structure of LiNi_1/3Co_1/3Mn_1/3O₂ was not affected by the Al₂O₃ coating. However, the Al₂O₃ coatings on LiNi_1/3Co_1/3Mn_1/3O₂ improved the cyclic life performance and rate capability without decreasing its initial discharge capacity. These electrochemical properties were also compared with those of LiAlO₂-coated LiNi_1/3Co_1/3Mn_1/3O₂ cathode material. The electrochemical impedance spectroscopy (EIS) was studied to understand the enhanced electrochemical properties of the Al₂O₃-coated LiNi_1/3Co_1/3Mn_1/3O₂ compared to uncoated LiNi_1/3Co_1/3Mn_1/3O₂.     

Effect of arc current on microstructure,texturing and wear behavior of plasma sprayed CaZrO3 coatings

In order to enhance the biocompatibility of metallic implants, various ceramic coatings are currently in vogue. CaZrO₃, a promising candidate material, was deposited through plasma spraying on stainless steel (316L) substrates at arc currents of 400, 500 and 600 A. The coatings were characterized using a SEM, XRD, surface profilometers and a tribometer. It was found that the arc current had profound effects on the thickness, microstructure, phase evolution, crystallinity and wear behavior of the coatings. The cross-sectional images and fractographic analysis showed that a denser coating with better inter-splat fusion was produced at arc current of 600 A. The average roughness (Ra) of the coatings increased from 3.62 to 6.68 μm as the arc current was increased from 400 to 600 A. The feedstock (powder) and the coatings were predominantly composed of CaZrO₃ along with a minor amount of CaZr₄O₉ phase. The rise in the arc current resulted in a slight increase in the relative proportion of the CaZrO₃ phase. Also, the coating produced at arc current of 600 A exhibited highest crystallinity. The detailed XRD analysis of (002) and (200) reflections of the ferroelectric CaZrO₃ revealed the preferred orientation of crystals in the coatings. The presence of this texture is explained on the basis of shifting the unstable Zr⁴⁺ ion in oxygen octahedral cage preferably in one direction. The increase in the arc current decreased the coefficient of friction and, as a result, relatively better wear resistance was observed for the coating produced using higher arc current. Moreover, the coating fabricated using arc current of 600 A reduced the volumetric weight loss by 13 times during the wear test as compared to the substrate. Plasma sprayed CaZrO₃ coating not only enhanced the wear resistance of the stainless steel but also showed the potential to furnish a bioactive surface.     

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.     

Evaluation of hot corrosion behavior of CSZ,CSZ/micro Al2O3 and CSZ/nano Al2O3 plasma sprayed thermal barrier coatings

Hot corrosion is one of the main destructive factors in thermal barrier coatings (TBCs) which come as a result of molten salt effect on the coating–gas interface. Hot corrosion behavior of three types of plasma sprayed TBCs was evaluated: usual CSZ, layer composite of CSZ/Micro Al₂O₃ and layer composite of CSZ/Nano Al₂O₃ in which Al₂O₃ was as a topcoat on CSZ layer. Hot corrosion studies of plasma sprayed thermal barrier coatings (TBCs) were conducted in 45 wt% Na₂SO₄+55 wt% V₂O₅ molten salt at 1050 °C for 40 h. The graded microstructure of the coatings was examined using scanning electron microscope (SEM) and X-ray diffractometer (XRD) before and after hot corrosion test. The results showed that no damage and hot corrosion products was found on the surface of CSZ/Nano Al₂O₃ coating and monoclinic ZrO₂ fraction was lower in CSZ/Micro Al₂O₃ coating in comparison with usual CSZ. reaction of molten salts with stabilizers of zirconia (Y₂O₃ and CeO₂) that accompanied by formation of monoclinic zirconia, irregular shape crystals of YVO₄, CeVO₄ and semi-cubic crystals of CeO₂ as hot corrosion products, caused the degradation of CSZ coating in usual CSZ and CSZ/Micro Al₂O₃ coating.     

Deposition behavior and characteristics of hydroxyapatite coatings on Al2O3, Ti,and Ti6Al4V formed by a chemical bath method

A simple chemical bath method was used to deposit hydroxyapatite (HA) coatings on Al₂O₃, Ti, and Ti6Al4V substrates at ambient pressure by heating to 65–95 °C in an aqueous solution prepared with Ca(NO₃)₂·4H₂O, KH₂PO₄, KOH, and EDTA. The deposition behavior, morphology, thickness, and phase of the coatings were investigated using scanning electron microscopy and X-ray diffractometry. The bonding strength of the coatings was measured using an epoxy resin method. The HA coatings deposited on the three kinds of substrates were fairly dense and uniform and exhibited good crystallinity without any additional heat treatment. A coating thickness of 1–1.8 μm was obtained for the samples coated once. By repeating the coating process three times, the thickness could be increased to 4.5 μm on the Al₂O₃ substrate. The bonding strength of these coatings was 18 MPa.     

Improvement of interface between Al and short carbon fibers by α-Al2O3 coatings deposited by sol–gel technology

This paper describes an investigation on an improvement of the interface between Al and short carbon fibers (SCFs) with α-Al₂O₃ coating by sol–gel technology. The composites of Al/uncoated SCFs and Al/α-Al₂O₃-**coated SCFs were fabricated successfully by vacuum press infiltration. The formation of α-Al₂O₃ coating during calcination was analysed by Fourier transform infrared (FTIR) and X-ray diffraction (XRD). Scanning electron microscopy (SEM), energy-dispersive analysis of X-ray (EDAX) and transmission electron microscope (TEM) were used to observe the coated SCFs and the interface of composites. The results showed that the average thickness of the α-Al₂O₃ coating was about 200–250 nm and the formation of Al₄C₃ at the interface between Al matrix and SCFs was controlled by the α-Al₂O₃ coatings.     

Preparation and corrosion resistance studies of nanometric sol-gel-based CeO2 film with a chromium-free pretreatment on AZ91D magnesium alloy

Magnesium alloy, although valuable, is reactive and requires protection before it can be applied in many fields. In this study, a novel protective environmental-friendly gradient coating was performed on AZ91D magnesium alloy by non-chromate surface treatments, which consisted of phytic acid chemical conversion coating and the sol-gel-based CeO₂ thin film. The surface morphologies, microstructure and composition of the coatings were investigated by scanning electron microscopy (SEM), energy disperse spectroscopy (EDS) and X-ray diffraction (XRD), respectively. The corrosion resistance of the coatings was evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) in 3.5 wt.% NaCl solution. The effects of the concentration, layers, temperature of heat treatment of CeO₂ sol on the anti-corrosion properties of the gradient coating for magnesium were also investigated. The results showed that the gradient coating was mainly composed of crystalline CeO₂. According to the results of electrochemical tests, the corrosion resistance of AZ91D magnesium alloy was found to be greatly improved by means of this new environmental-friendly surface treatment.