Fabrication of corrosion-resistant Al2O3–CeO2 composite coating on AA7075 via plasma electrolytic oxidation coupled with electrophoretic deposition

Al₂O₃–CeO₂ composite coating was fabricated on AA7075 by combining plasma electrolytic oxidation (PEO) with electrophoretic deposition (EPD). CeO₂ nanoparticles are electrophoretically incorporated into the plasma electrolytic oxidized Al₂O₃ coatings by the synergetic effect of PEO and EPD processes. The passivation behavior of Al₂O₃ and inhibiting nature of CeO₂ have been studied by the electrochemical corrosion analysis in 3.5 wt% NaCl solution and salt spray corrosion test (SSCT) in 5 wt% NaCl as per ASTM standards. The results showed that the Al₂O₃–CeO₂ composite coating via PEO coupled EPD significantly improved the corrosion resistance (~10³ times higher R_p) compared to the plasma electrolytic oxidized Al₂O₃ coating.     

Effect of Y2O3 addition on tribological properties of plasma sprayed Al2O3-13% TiO2 coating

The effect of Y₂O₃ addition on structure, mechanical properties and tribological properties of Al₂O₃-13 wt% TiO₂ coating was investigated. The addition of 20 wt% Y₂O₃ resulted in better densification, stabilization of alpha (α) alumina phase and improvement in fracture toughness of Al₂O₃-13 wt% TiO₂ coating. Abrasive wear tests were performed over a range of loads and sliding speeds. The stabilization of α alumina phase further increased with an increase in severity of wear test conditions, as noted from X-Ray Diffraction (XRD) and X-Ray Photoelectron Spectroscopy (XPS) analysis of worn coatings. Al₂O₃-13 wt% TiO₂-20 wt% Y₂O₃ coating displayed lower friction coefficient and lower abrasive wear rate than Al₂O₃-13 wt% TiO₂ coating, which was due to synergistic effect of α alumina phase and formation of magneli phase oxide of titanium; Ti₂O₃. Friction energy map was used to rationalize observed wear rates, to identify different regimes of wear and degradation modes of coatings.     

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.     

Microstructure and interface-adhesion of thermally sprayed continuous gradient elastic modulus FeCrAl-ceramic coatings

The bond strength between thermally sprayed metal bond-coats and ceramic top-coats is a key factor in determining their service life. However, most studies focus on interface modifications. In this research, based on FeCrAl bond-coats prepared by arc spraying, top-coats (Al₂O₃-40 wt% TiO₂) were prepared by plasma spraying, and heat treatment was carried out in a hypoxic atmosphere. Continuous gradient elastic modulus FeCrAl-ceramic coatings were successfully prepared, and the microstructural and mechanical properties from the substrate to the top-coats were systematically investigated. The Al₂O₃ content gradually decreased from the top-coats to the substrate, forming continuous gradient elastic modulus FeCrAl-ceramic coatings. The oxide formed during the heat treatment filled the defects in the bond-coats and greatly improved the mechanical properties of the coating. The bonding strength of the continuous gradient elastic modulus coating was 21.7% greater than that of the as-received coating.     

Effect of CeO2 and Al2O3 contents on Ce‐ZrO2/Al2O3 composites

Effect of CeO₂ and Al₂O₃ contents on phase composition, microstructures, and mechanical properties of Ce–ZrO₂/Al₂O₃ composites was studied. The CeO₂ content in CeO₂–ZrO₂ varied from 7 to 16 mol%, and the Al₂O₃ content in Ce‐ZrO₂/Al₂O₃ composites were 7 and 22 wt%. When CeO₂ content was ≤10 mol%, high Al₂O₃ content contributed to hinder the tetragonal‐to‐monoclinic ZrO₂ phase transformation during cooling and decrease the density of microcracks in the composites. Tetragonal ZrO₂ single‐phase was obtained in the composites with ≥12 mol% CeO₂, regardless of the Al₂O₃ content. Hardness, flexural strength, and toughness were dependent on CeO₂ and Al₂O₃ contents which were related to the microcracks, grain size, and phase transformation. The high flexural strength and toughness of the composites with 7wt% Al₂O₃ could be obtained at an optimum CeO₂ content of 12 mol%, whereas those of the composites with 22 wt% Al₂O₃ could be achieved in the wide CeO₂ content range of 8.5‐12 mol%.     

Comprehensive study on corrosion protection properties of Al2O3, Cr2O3 and Al2O3–Cr2O3 ceramic coatings deposited by plasma spraying on carbon steel

In this study, individual Al₂O₃ and Cr₂O₃ coatings and Cr₂O₃-25, 50, 75 wt% Al₂O₃ composite coatings were applied on carbon steel by atmospheric plasma spraying method. Corrosion experiments were performed on as-sprayed and epoxy resin sealed coatings including potentiodynamic polarization, electrochemical impedance spectroscopy and long-term immersion in 3.5 wt% NaCl solution. Phase composition and microstructure of the coatings were investigated by x-ray diffraction, optical microscopy and scanning electron microscopy, before and after the corrosion experiment. The results showed that the Cr₂O₃ coating exhibited the best corrosion resistance, due to the densest microstructure and highest adhesion strength. The Cr₂O₃-25 wt% Al₂O₃ coating had the highest interconnected porosities and thus had the least corrosion resistance compared to other coatings. In general, the as-sprayed coatings induced a maximum increase of 3.93 times the polarization resistance (R_p) in the polarization experiment and a 3.5 times increase in the charge transfer resistance (R_ct) in the EIS experiment, which was not significant. Stresses caused by increased volume of corrosion products in the coating-substrate interface resulted in the spallation of Cr₂O₃-25, 50 wt% Al₂O₃ coatings from the substrate over long-term of immersion. The adhesion strength of the coatings was a determining criterion for the long-term durability of the coatings. The sealing treatment resulted in a significant increase in R_p and R_ct.     

Effect of CeO2 addition on the sintering behavior of pre-synthesized magnesium aluminate spinel ceramic powders

In this work, the effects of 1?wt%, 2?wt%, and 3?wt% CeO₂ as an additive on the sintering behavior of alumina-rich spinel and magnesia-rich spinel powders subjected to sintering at temperatures of 1600?°C, 1650?°C, 1700?°C, and 1750?°C were investigated. The sintering behavior of the ceramics was investigated according to dilatometry measurements, linear shrinkage, bulk density, phase analysis, and microstructure. It was demonstrated that CeO₂ hindered the sintering process in alumina-rich spinel by reacting with Al₂O₃ exsolved from the spinel to form platelet-shaped particles of CeAl₁₁O₁₈ interspersed between the spinel grains. Meanwhile, the presence of CeO₂ promotes the sintering process in magnesia-rich spinel by being distributed in an isolated form among the spinel grains.     

Experimental investigation of Al2O3/8YSZ and CeO2/8YSZ plasma sprayed thermal barrier coating on diesel engine

In this research work, aluminium oxide/yttria stabilized zirconia (20%Al₂O₃/80%8YSZ) and ceria/yttria stabilized zirconia (20%CeO₂/80%8YSZ) were coated through atmospheric plasma spray technique (APS) as thermal barrier coating (TBC) over CoNiCrAlY bond coat on aluminium alloy (Al-13%Si) substrate piston crown material and their thermal cycling behavior were studied experimentally. Thermal cycle test of both samples were conducted at 800?°C. Microstructural, phase and elemental analysis of the TBC coatings were experimentally investigated. The performance, combustion and emission characteristics of Al₂O₃/8YSZ, CeO₂/8YSZ TBC coated and uncoated standard diesel engine were experimentally investigated. The test results revealed that CeO₂/8YSZ based TBC has an excellent thermal cycling behavior in comparison to the Al₂O₃/8YSZ based TBC. The spallation of the Al₂O₃/8YSZ TBC occurred mainly due to the formation of thermally grown oxide (TGO), and growth of residual stresses at top coating and bond coating interface. The experimental results also revealed that the increase of brake thermal efficiency and reduction of specific fuel consumption for both TBC coated engine. Further reduction of HC, CO and smoke and increase of NOx emission were recorded for both TBC coated engine compared to the standard diesel engine.     

Impact of Al2O3-40 wt.% TiO2 feedstock powder characteristics on the sprayability,microstructure and mechanical properties of plasma sprayed coatings

Atmospheric plasma sprayed (APS) Al₂O₃-TiO₂ coatings have found a wide range of industrial application due to their favorable properties, combined with low costs and a high availability. However, the detailed effect of the phase composition and the element distribution of the feedstock powders on the coating properties and the spraying process have only crudely been investigated so far. Here the impact of aluminum titanate (Al₂TiO₅) on the microstructural features and mechanical properties of Al₂O₃-40 wt.% TiO₂ APS coatings is demonstrated by investigating the detailed phase composition and the distribution of aluminum and titanium in three fused and crushed feedstock powders and the respective coatings. Thereby, a direct influence of Al₂TiO₅ content on the deposition efficiency, the porosity, the elastic modulus, and the hardness of the coatings is revealed. The results emphasize the need for a more detailed specification of commercial Al₂O₃-TiO₂ feedstock powders to ensure a high reliability of the coating properties.     

Preparation and characterization of Ce-ZrO2/Al2O3 composites by DLP-based stereolithography

This work investigates the printability of Ce-ZrO₂/Al₂O₃ composites through a Digital Light Processing (DLP) technology. Commercially available 10 mol% CeO₂ and 12 mol% CeO₂-stabilized zirconia were mixed with alumina powders, to provide 11 mol% CeO₂-stabilized ZrO₂/16 vol% Al₂O₃ (Ce-ZA₁₆) composite materials. The powders were dispersed under wet conditions, and the homogeneous nanometric dispersion was maintained once added into the liquid monomer. Slurries at several solid loadings were explored, with and without dispersant addition. First, the key role of the dispersant to significantly enhance the solid loading and thus the sintered density was demonstrated. Second, among different dispersant-added slurries at various solid loadings, ranging from 65 to 80 wt%, the best compromise between rheological behavior and curing depth was established. The best formulations, comprised between 70 and 80 wt%, successfully provided fully dense and completely homogeneous composites.     

Protective properties of Al2O3 + TiO2 coating produced by the electrostatic spray deposition method

Mechanical resistance of Al₂O₃ + TiO₂ nanocomposite ceramic coating deposited by electrostatic spray deposition method onto X10CrAlSi18 steel to thermal and slurry tests was investigated. The coating was produced from colloidal suspension of TiO₂ nanoparticles dispersed in 3 wt% solution of Al₂(NO₃)₃, as Al₂O₃ precursor, in ethanol. TiO₂ nanoparticles of two sizes, 15 nm and 32 nm, were used in the experiments. After deposition, coatings were annealed at various temperatures, 300, 1000 and 1200 °C, and next exposed to cyclic thermal and slurry tests. Regardless of annealing temperature and the size of TiO₂ nanoparticles, the outer layer of all coatings was porous. The first five thermal cycles caused a rapid increase of aluminum content of the surface layer to 30–37 wt%, but further increase in the number of thermal cycles did not affect the aluminum content. The oxidation rate of coating-substrate system was lower during the thermal tests than during annealing. The oxidation rate was also lower for smaller TiO₂ particles (15 nm) forming the coating than for the larger ones (32 nm). The protective properties of Al₂O₃ + TiO₂ coating against intense oxidation of substrate were lost at 1200 °C. Slurry tests showed that coatings annealed at 1000 °C had the best slurry resistance, but thermal tests had weakened this slurry resistance, mainly due to decreasing adhesion of the coating.     

Al2O3/CrAlSiN multilayer coating deposited using hybrid magnetron sputtering and atomic layer deposition

In this study, Al₂O₃/CrAlSiN multilayer coatings with various periods were prepared using a hybrid process involving overlapping magnetron sputtering of CrAlSiN and atomic layer deposition (ALD) of Al₂O₃. The influence of the number of Al₂O₃ layers on the mechanical properties, corrosion behavior and oxidation characteristics of the coatings was studied using nano/micro indentation, electrochemical corrosion, and high temperature static oxidation tests. The results show that the multilayer structure can effectively prevent crack propagation during the coating and subsequently increase the coating toughness. A substantial improvement in the resistance to electrochemical and oxidation corrosion was observed in the Al₂O₃/CrAlSiN multilayer coatings and increasing the number of Al₂O₃ layers dramatically increases the corrosion durability. The Al₂O₃ ALD layers are expected to inhibit the diffusion of corrosive substances such as ions and oxygen and the increase of the Al₂O₃ layer number decreases the diffusion fluxes of the coating elements to the surface and limit the oxide growth, resulting in the evolution of the oxidation produces from irregular particles to nano-walls/fibers. It is supposed that the PVD/ALD hybrid process may open a new hard coating design concept by providing a superior toughness and corrosion/oxidation resistance.     

Low pressure plasma-sprayed Al2O3 and Al2O3/SiC nanocomposite coatings from different feedstock powders

This paper describes a preliminary investigation of a nanocomposite ceramic coating system, based on Al₂O₃/SiC. Feedstock Al₂O₃/SiC nanocomposite powder has been manufactured using sol-gel and conventional freeze-drying processing techniques and then low pressure plasma sprayed onto stainless steel substrates using a CoNiCrAlY bond coat. Coatings of a commercial Al₂O₃ powder have also been manufactured as a reference for phase transformations and microstructure. The different powder morphology and size distribution resulting from the different processing techniques and their effect on coating microstructure has been investigated. Phase analysis of the feedstock powders and of the as-sprayed coatings by X-ray diffractometry (XRD) and nuclear magnetic resonance (NMR) showed that the nano-scale SiC particles were retained in the composite coatings and that equilibrium α-Al₂O₃ transformed to metastable γ- and δ-Al₂O₃ phases during plasma spraying. Other minority phases in the sol-gel Al₂O₃/SiC nanocomposite powder such as silica and aluminosilicate were removed by the plasma-spraying process. Microstructure characterisation by scanning electron microscopy (SEM) of the as-sprayed surface, polished cross-section, and fracture surface of the coatings showed evidence of partially molten and unmolten particles incorporated into the predominantly lamella microstructure of the coating. The extent of feedstock particle melting and consequently the character of the coating microstructure were different in each coating because of the effects of particle morphology and particle size distribution on particle melting in the plasma.     

Effect of in-situ oxidation on the nanomechanical evolution of Fe-base coating with ceramic particles produced by internal rotating plasma spraying

In this work, we investigated FeCrMo coatings with 35 wt% ceramic, which were produced on a cylinder surface by an internal rotating plasma spraying and oxidized in air. The ceramic particles consisted of 80 wt% alumina and 20 wt% zirconia, which can improve the mechanical properties of the coating. For microstructural characterization, scanning electron microscopy was combined with energy dispersive X-ray analysis and electron probe micro analysis, and the nanomechanical properties were measured by a nanoindentation tester. The structure of Fe-base coating matrix consists of Al₂O₃, ZrO₂ and a small amount of mixed Fe–Cr oxides, and the ceramic particles exhibit a uniform distribution. During oxidation, a mixed oxide layer containing Fe₂O₃ and Fe₃O₄ forms on the surface of the Fe-base coating, and the thickness of the oxide layer increases with increasing oxidation temperature. Due to the in-situ oxidation, the nanohardness and Young's modulus of the Fe-base coating decreased with increasing oxidation temperature. The nanohardness evolution of Fe-base coatings oxidized at different temperatures is discussed.     

Mechanical and tribological properties of nano/micro composite alumina coatings fabricated by atmospheric plasma spraying

Adding nano particles can significantly improve the mechanical properties and wear resistance of thermal sprayed Al₂O₃ coating. However, it still remains a challenge to uniformly incorporate nano particles into traditional coatings due to their bad dispersibility. In the present work, nanometer Al₂O₃ (n-Al₂O₃) powders modified by KH-560 silane coupling agent were introduced into micrometer Al₂O₃ (m-Al₂O₃) powders by ultrasonic dispersion to afford nano/micro composite feedstock, and then four resultant coatings (weight fraction of n-Al₂O₃: 0%, 3%, 5% and 10%) were fabricated by atmospheric plasma spraying. The features and constitutes of feedstock and as-sprayed coatings, as well as their porosity, bonding strength, microhardness and frictional behaviors were investigated in detail. Results show that the nano/micro composite feedstock with uniform microstructure can be better melted in the spraying process, thereby obtaining coatings with denser microstructure, higher hardness and bonding strength. Added n-Al₂O₃ has no obvious effect on the friction coefficient of composite coatings, whereas can improve their wear-resistant and reduce the worn degree of counterpart. The wear mechanism of traditional coating is brittle fracture and lamellar peeling, while that of composite coating with weight fraction of n-Al₂O₃ of 10% is adhesive wear.     

Synthesis and characterization of corrosion-resistant and biocompatible Al2O3–TiB2 nanocomposite films on pure titanium

Alumina is widely used as a coating on a metal implant due to its favorable mechanical and biological properties. In this research, in order to improve mechanical and biological properties of alumina, a composition of nanoparticles of alumina (instead of microparticles) and titanium diboride micro powder is introduced. The atmospheric plasma spray (APS) technique was applied to deposit Al₂O₃–TiB₂ on the pure titanium substrate. The properties of Al₂O₃–TiB₂ nanocomposite coatings with various weight percent of TiB₂ (20, 30 and 40 wt%) were experimentally studied. The characteristics of nanocomposite films of TiB₂ (20, 30 and 40 wt%) were analyzed using Field Emission Scanning Electron Microscopy (FE-SEM), energy dispersive electron spectroscopy (EDX) and X-Ray Diffraction (XRD) tests. The XRD spectra exhibited that in addition to alumina and titanium diboride, the films contained titania. Thickness and morphology of the films were calculated from FE-SEM images and the thickness of the optimized coating (Al₂O₃-30 wt% TiB₂) was about 30–45 μm. Also, the roughness, corrosion resistance, hardness and cytotoxicity (MTT) tests were studied. The highest of hardness and roughness of the samples were obtained from Al₂O₃-30 wt% TiB₂. According to the obtained results from the polarization test, Al₂O₃-30 wt% TiB₂ coating had the highest corrosion resistance (222558.9962 Ω cm²). Therefore, the toxicity of Al₂O₃-30 wt% TiB₂ was investigated as the optimized coating and the results confirmed its non-toxicity and biocompatibility.     

Promoting effect of Pt addition to Ni/CeO2/Al2O3 catalyst for steam gasification of biomass

The modification of Ni/CeO₂/Al₂O₃ with Pt can make the activation by H₂ reduction unnecessary, and this indicates that the Pt/Ni/CeO₂/Al₂O₃ catalyst can be activated automatically by the compounds contained in tar. This can be explained by the enhancement of the Ni reducibility by the addition of Pt. The results of the temperature programmed reduction with H₂ also support this enhancement. Furthermore, the addition of 0.1% Pt to Ni/CeO₂/Al₂O₃ (4 wt% Ni, 30 wt% CeO₂) enhanced the performance in the steam gasification of biomass, compared to Ni/Al₂O₃ and Ni/CeO₂/Al₂O₃ in terms of low tar yield and high gas yield. This can be related to the Pt–Ni alloy formation indicated by the extended X-ray absorption fine structure analysis.     

In-situ generation and application of nanocomposites on steel surface for anti-corrosion coating

Thin organic coatings directly on steel sheets provide excellent barrier protection in saline environment and meet deformability demands, but fail in providing active corrosion protection. We have put an effort to solve this problem by formulating composite coatings using in-situ generation of metal oxide nanoparticles (NPs) in the polymer matrix. Here we present a new synthesis method of high performance polyetherimide composite with TiO₂, MgO, and Al₂O₃ nanoparticles and their application for anti-corrosion coatings in saline environment. We observed that in-situ synthesis of these metal oxide NPs in the polymer curing process leads to evenly distribution and uniform size of nanoparticles. Thermo-mechanical property was analyzed for these three kinds of free-standing composite film to assess elasto-plastic behaviour and compared to mother polymer film. Results indicated that thermal stability and elastic behaviour of composites film are not affected to the great extent by the presence of NPs. The potentiodynamic and the electrochemical impedance studies on these composite coated steel panels were carried out to identify active–passive behaviour. Results showed active corrosion protection from nanocomposite coating based on TiO₂ and barrier protection was noticed from nanocomposite coating based on MgO and Al₂O₃.     

Influence of Y2O3 on the microstructure and tribological properties of Ti-based wear-resistant laser-clad layers on TC4 alloy

Multi-track Ti-based wear-resistant composite coatings were fabricated on TC4 alloy surfaces using laser-clad TC4 + Ni45 + Co–WC mixed powders with different Y₂O₃ contents (0, 1, and 3 wt%). The microstructure, microhardness, and tribological properties of the coatings were characterised using X-ray diffraction, scanning electron microscopy, energy dispersive spectrometry, electron probe X-ray micro analyser, microhardness tester, and friction and wear testing apparatus. The results showed that the number of cracks on the coating surfaces gradually decreased with the addition of Y₂O₃ and that residual Co–WC powders existed in the coating subsurfaces. The phase composition of the coatings with different Y₂O₃ contents remained unchanged and was mainly composed of reinforcing phases of TiC, TiB₂, Ti₂Ni, and matrix α-Ti. With the addition of Y₂O₃, the coating microstructure was remarkably refined, the direction characteristic of the TiC dendrites obviously weakened, and the nucleation rate significantly increased. When the added Y₂O₃ was 3 wt%, a large amount of TiB₂–TiC-dependent growth composite phases precipitated in the coating. The two-dimensional lattice misfit between (0001)_TiB2 and (111)_TiC was 0.912%, which indicated that TiB₂ and TiC formed a coherent interface. When the amount of Y₂O₃ was increased, the microhardness of the coatings gradually decreased, and the wear volume of the coatings first increased and then decreased. Under the effect of the TiB₂–TiC composite phases, the wear resistance of the 3 wt% Y₂O₃ coating was optimal. The 3 wt% Y₂O₃ coating friction coefficient was the lowest, and the wear mechanism was abrasive wear.     

Correlation between microstructure,chemical components and tribological properties of plasma-sprayed Cr2O3-based coatings

The wear resistance of chromium oxide (Cr₂O₃) coatings could be improved by doping modification and changing the structural scale, etc. In this study, micrometric Cr₂O₃ coatings were doped with different additives, CeO₂ and Nb₂O₅. Moreover, Cr₂O₃ coatings were deposited from nanostructured feedstock by the combination process of plasma spraying and dry-ice blasting. The correlation between the microstructure, chemical components and tribological properties of plasma-sprayed Cr₂O₃-based coatings was discussed based on the investigation of their porosity, hardness and friction behaviors. The results showed that the composite coatings doped with additives exhibited a higher microhardness, corresponding to a lower porosity than pure Cr₂O₃ coating under the identical plasma-spray condition. CeO₂ constituent was found to improve the wear resistance of Cr₂O₃ coating while Nb₂O₅ incorporation corresponds to a steep rise in the friction coefficient. The mismatch of coefficient of thermal expansion (CTE) between Cr₂O₃ and Nb₂O₅ lamellae facilitated the origin of fatigue cracks and the formation of microfracture pits. Although the combination process promotes a porosity reduction, the nanostructured Cr₂O₃ (n-Cr₂O₃) coatings present a lower microhardness than micrometric coatings, due to their loosen microstructure from insufficient plasma power compared to microscaled coatings. The wear mechanisms of both the micro- and nanometric Cr₂O₃ coatings are fatigue cracks and material transfer.