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.     

Formation mechanism of Al2O3-YAG amorphous ceramic coating deposited via atmospheric plasma spraying

Al₂O₃-YAG (Al₅Y₃O₁₂) amorphous ceramic coatings exhibit excellent crack propagation resistance under harsh wear services due to the amorphous phase contributing to the plastic deformation performance of the coating. However, the formation mechanism of the amorphous phase is ambiguous. This study mainly investigated the formation mechanism of Al₂O₃-YAG amorphous coating prepared by atmospheric plasma spraying from the perspective of crystallization chemistry. Nano and microsized powders with low eutectic point ratio were selected as feedstock for comparison. X-ray diffraction, scanning electron microscope, and electron backscattered diffraction were used to analyze the phase composition, morphologies, phase distribution, and structure of the coating. It is concluded that the significant thermodynamically stable structure of polycompound with high coordination numbers of cations prioritized crystallizing in the Al₂O₃-YAG melt, but it needed more time to crystallize and hardly crystallized in the limited time during plasma spraying. Therefore, the selection of as-sprayable powder should also be considered the critical factor for preparing amorphous coatings. The nanoscale or submicro scale powder distributed uniformly with low eutectic point ratio was chosen as the feedstock to ensure the powder droplets diffuse sufficiently during deposition.     

Effect of the powder particle structure and substrate hardness during vacuum cold spraying of Al2O3

In this paper, the effect of the powder particle structure and substrate hardness during vacuum cold spraying (VCS) of Al₂O₃ is investigated. Our results help understand the underlying deposition mechanism during VCS in more detail and enable the tailoring and improving of the resulting coatings. Two structurally different alumina feedstocks were used for this study. We find that the loosely agglomerated powder bonds to the substrate primarily through coordinated deformation of the nano-sized powder particles. The sintered powder, on the other hand, bonds to the substrate through severe fracture and deformation of the particles. High-resolution transmission electron microscopy (HR-TEM) was employed to observe details in the interfacial microstructure of the coatings on the two substrates with differing hardness. The hard steel substrate facilitates particle fracture, which leads to cohesive particle/particle-bonding in the coating region close to the substrate. The softer aluminum substrate leads to strong interfacial coating/substrate-bonding because the particles are embedded into the substrate. In summary, the fracture and deformation of the feedstock as well as the substrate hardness affect both adhesion (coating/substrate bonding) and cohesion (particle/particle bonding) considerably.     

Effect of plasma sprayed and laser re-melted Al2O3 coatings on hardness and wear properties of stainless steel

Commercially available austenic stainless steel substrate was coated with commercially available, raw Al₂O₃ powder applied by means of plasma spraying method and then re-melted with CO₂ laser beam of various parameters. Tribological and mechanical properties of the 120 J/mm and 160 J/mm laser re-melted coatings were compared with the tribological and mechanical properties of the “as-sprayed” coating. The influence of the laser beam of various parameters on the microstructure, phase constituents, and mechanical and tribological properties of the ceramic coating was investigated by means of scanning electron microscopy, light microscopy, computer tomography, X-ray diffraction technique and nanoindentation tests. The micro sliding wear performance of the coatings was tested using a nanoindenter. The study showed an improvement of the mechanical and tribological properties caused by the laser treatment. The best results were achieved for coating re-melted with 120 J/mm laser beam.     

Corrosion resistance of Al2O3-Y2O3-SiC coating on depleted uranium prepared by cathode plasma electrolytic deposition

Al₂O₃-Y₂O₃-SiC composite coatings were prepared on depleted uranium by cathode plasma electrolytic deposition in Al(NO₃)₃, Y(NO₃)₃, SiC nanoparticles and anhydrous ethyl alcohol mixture. The resulting coating consisted of an inner barrier layer and an outer porous layer. The SiC nanoparticles were incorporated into the composite coating and decreased the coating porosity by filling the pores. The potentiodynamic polarization test and neutral salt spray test revealed that the corrosion resistance of depleted uranium was enhanced by the composite coating. Moreover, with increasing the content of SiC nanoparticles in the coating, the coating corrosion resistance was improved gradually.     

Comparison of dry sliding wear behavior of plasma sprayed FeCr slag coating with Cr2O3 and Al2O3-13TiO2 coatings

The microstructure and dry sliding wear performance of thermally sprayed FeCr slag coating were evaluated in comparison with those of commercially available Al₂O₃-13TiO₂ and Cr₂O₃ ceramic coating powders to assess the applicability of FeCr slag (FS) powder, fabricated from industrial waste, as a ceramic top-coating material against wear. Ceramic top coats and underlying NiCoCrAlY bond coats were deposited on AISI 316L samples via atmospheric plasma spraying (APS), and their tribological properties were assessed using a ball-on-disc test rig at room temperature. As a result, FS coating exhibited the lowest worn volume, although it has the lowest surface hardness. Tribolayer formation was observed on the surface of the samples which were subjected to dry sliding wear tests. Delamination type wear is the dominant wear mechanism for Cr₂O₃ and FS coatings, whereas local spallation areas arising from plastic deformation were observed on the surface of Al₂O₃-13TiO₂ coatings. The results suggested the applicability of FS powder as a candidate ceramic top coating material against wear.     

In situ (Al,Cr)2O3-Cr composite coating fabricated by reactive plasma spraying

In situ (Al,Cr)₂O₃-Cr composite coating was fabricated by reactive plasma spraying Al-Cr₂O₃ composite powder. Phase composition and microstructure of the as-sprayed coating was characterized by X-ray diffractometer, scanning electron microscope and transmission electron microscope. Indentation fracture behavior of the coating was investigated. It is found that the microstructure of the coating consists of [(Al,Cr)₂O₃+Cr] eutectic and Cr+[(Al,Cr)₂O₃+Cr] hypoeutectic. The eutectic microstructure of the coating shows the characteristic of nano structure, in which Cr particles with size less than 40 nm distribute in (Al,Cr)₂O₃ solid solution matrix. The hypoeutectic microstructure of the coating consists of Cr particles with size larger than 1 µm and [(Al,Cr)₂O₃+Cr] divorced eutectic. The toughness of the (Al,Cr)₂O₃-Cr composite coating is significantly improved compared with that of the conventional Al₂O₃ coating.     

Aqueous suspension processing of multicomponent submicronic Y-TZP/Al2O3/SiC particles for suspension plasma spraying

In order to obtain thermal barrier coatings by Suspension Plasma Spraying (SPS) process with potential new self-healing ability multicomponent submicronic Y-TZP/Al₂O₃/SiC suspensions were prepared. For this purpose, concentrated aqueous suspensions of individual components, as well as the multicomponent mixture were studied and characterised, in terms of colloidal stability and rheological behaviour to determine the best conditions for processing and preparation of the coatings. In the study, different dispersant contents and sonication times were tested. Subsequently, low concentrated suspensions were prepared to obtain preliminary thermal barrier coatings with the optimised feedstock. Thus, ceramic coatings were deposited by SPS and then characterised in order to assess the microstructure and phase distribution, in particular, the degree of preservation of the sealing agent, SiC, in the final coating as a previous indicator of its self-healing ability.     

Influence of different introduction modes of metal Ag into plasma sprayed Al2O3 coating on tribological properties

Al₂O₃ coating and Al₂O₃/Ag (10%) composite coating were prepared on the surface of GH4169 superalloy by the atmospheric plasma spraying technology. And an in-situ synthesis method was applied to introduce the Ag particles into a part of Al₂O₃ coatings to obtain Al₂O₃/Ag(synthesis) composite coating. Then, the microstructure and mechanical properties of these three Al₂O₃-based coatings were systematically studied in this work. In order to reveal the lubrication characteristics of Ag, their friction tests were carried out at room temperature (RT), 400 °C, 600 °C and 800 °C, respectively. The results showed that both microstructure and mechanical properties of Al₂O₃/Ag(synthesis) composite coating were better than that of Al₂O₃/Ag (10%) composite coating because many pores and cracks produced during the direct spraying. Although the friction coefficients of two kinds of composite coatings were close to that of Al₂O₃ coatings at RT, their wear rates were both greatly decreased due to the introduction of Ag. In addition, the lubricating performance of Ag was not enough to reduce their friction coefficients when friction temperature is lower than 600 °C. However, the friction coefficients of these composite coatings were both reduced to about 0.3 at 800 °C . At this time, the Al₂O₃/Ag(synthesis) composite coating also exhibited a lower wear rate because of its dense microstructure and excellent mechanical properties.     

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.     

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.     

Microstructure and properties of niobium carbide composite coatings prepared by plasma spraying

Niobium carbide composite coatings were prepared on titanium alloy surface by plasma spraying NbC–Al₂O₃, Nb–SiC and Nb–SiC–Al composite powders, respectively. The phase composition, microstructure and formation mechanism of the three composite coatings were analyzed and their microhardness, toughness and scratch resistance were compared. The phases of the NbC–Al₂O₃ system did not change during the plasma spraying process, and new phases (Nb₂C, NbC and Nb₃Si) were formed in the Nb–SiC and Nb–SiC–Al systems. TEM results of the Nb–SiC composite coating indicate that the new phases nanocrystalline Nb₂C, submicron NbC and nanocrystalline Nb₃Si were formed during the plasma spraying process. Compared with the NbC–Al₂O₃ composite coating, the microstructure of the Nb–SiC and the Nb–SiC–Al composite coatings were uniform, and the porosity were relatively low, and the hardness was higher. The Nb–SiC–Al composite coating was denser than the Nb–SiC composite coating, the lamellar structure was obvious and the number of pores in the coating was the least, which is attributed to the better molten state of the composite powder by the addition of the Al to the Nb–SiC system. The Nb–SiC–Al composite coating had better toughness and scratch resistance.     

Gelcasting and pressureless sintering of silicon carbide ceramics using Al2O3–Y2O3 as the sintering additives

In this paper, silicon carbide ceramics were prepared by aqueous gelcasting and pressureless sintering using Al₂O₃ and Y₂O₃ as the sintering additives. In order to develop well dispersed SiC slurries in the presence of sintering additives, the Al₂O₃ and Y₂O₃ powder was treated in the citric acid solution in advance. Zeta potential measurement showed that the isoelectric point (IEP) of Al₂O₃ and Y₂O₃ powder moved toward low pH region after treatment. Rheological measurement confirmed that the addition of as-treated powder showed very limited influence on the slurry properties as compared to that of untreated powder. SiC slurries with solid content of 54 vol% and enough fluidity can be developed. After gelcasting and pressureless sintering, SiC ceramics with nearly full density, fine grained and homogeneous microstructure can be obtained. Results showed that the surface treatment of Al₂O₃ and Y₂O₃ with citric acid is effective for the gelcasting process of SiC.     

Fabrication of Si3N4 ceramics by post-reaction sintering using Si–Y2O3–Al2O3 nanocomposite particles prepared by mechanical treatment

Post-reaction sintering of a powder compact of Si and sintering aids is a useful technique for fabricating silicon nitride (Si₃N₄) ceramics at low costs. In order to inhibit the inhomogeneous and uncontrollable exothermic nitridation of Si in the powder compact, Si–Y₂O₃–Al₂O₃ nanocomposite particles are designed as an aid for post-reaction sintering. These Si–Y₂O₃–Al₂O₃ nanocomposite particles are prepared via mechanical treatment applying high shear stress. Scanning electron microscopy (SEM) observations show that Y₂O₃ and Al₂O₃ particles are homogenously dispersed, and fixed to the Si particles. A green compact prepared using the Si–Y₂O₃–Al₂O₃ nanocomposite particles results in lower electrical resistivity than that prepared using a powder mixed by wet ball-milling, which suggests that Si particles in the green compact prepared using the nanocomposite particles are isolated by Y₂O₃ and Al₂O₃ particles. The isolation of Si particles by the sintering aids successfully prevents the Si particles from melting and agglomerating during the nitridation process, resulting in a higher nitridation ratio and higher α-Si₃N₄ phase content due to the inhibition of rapid heat transfer caused by the exothermic reaction. The nitridation ratio also increases with the applied power during mechanical treatment. As a result of firing the homogeneously nitrided powder compacts at high temperatures, Si₃N₄ ceramics with homogeneous microstructure and improved density are successfully fabricated in this manner.     

Influence of Ca/Al ratio on physical and dielectric properties of Al2O3/CaO-B2O3-SiO2 glass-ceramics composite coatings prepared by high enthalpy atmospheric plasma spraying

The dielectric layer plays a key role in regulating electromagnetic wave broadband scattering based on meta-surface technology. Herein, the physical properties of composite powder, prepared by spray drying of CaO-B₂O₃-SiO₂ (CBS) glass-ceramic powder and Al₂O₃ in different mass ratios, are systematically investigated. Meanwhile, a high enthalpy atmospheric plasma spraying equipment is utilized to prepare CBS/Al₂O₃ composite coatings, and the morphology, physical properties and dielectric properties of the composite coating are analyzed. The XRD and DSC data of the composite coating reveal that the crystallization behavior of β-CaSiO₃ and CaB₂O₄ gradually disappear with the increase of Al₂O₃ content. Hence, only CaAl₂Si₂O₈ phase is observed during heat treatment. The experimental results confirm that the dielectric properties of CBS/Al₂O₃ composite coating conform to the rule of mixture for composite materials. Also, the dielectric properties are affected by porosity and crystallization rate.     

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.     

Effects of residual stress and intragranular particles on mechanical properties of hot-pressed Al2O3/SiC ceramic composites

Al₂O₃/SiC ceramic composites with different SiC contents have been prepared by powder metallurgy at 1600 °C for 120 min at 30 MPa pressure. The effect of second phase particles on the microstructure and mechanical properties of composites have been studied. The results show that SiC particle has a significant impact on the matrix subjected to residual stress, and on the microstructure of the composites as well. The average grain size of alumina matrix decreases as the SiC particle content increases. Simultaneously, it has been found that the mechanical properties of the material are significantly enhanced in comparison with monolithic Al₂O₃. The highest strength and toughness are obtained when the SiC content is 15 vol%, and the values are 1237 MPa and 5.68 MPa m^1/2, respectively. The mechanisms of strengthening and toughening have been discussed.     

Infrared radiative performance and anti-ablation behaviour of Sm2O3 modified ZrB2/SiC coatings

To improve the emissivity of ZrB₂/SiC coatings for serving in more serious environment, ZrB₂/SiC coatings with varying contents of high emissivity Sm₂O₃ were fabricated using atmospheric plasma spraying. The microstructure, infrared radiative performance and anti-ablation behaviour of the modified coatings were investigated. The results showed that as the content of Sm₂O₃ increased, the density of the coatings increased because of the low melting point of Sm₂O₃. When the content of Sm₂O₃ was 10 vol%, the coating had the highest emissivity in the 2.5–5 μm band at 1000 °C, up to 0.85, because of the oxygen vacancies promoting additional electronic transitions. Due to the high emissivity, the surface temperature of the coating modified with 10 vol% Sm₂O₃ decreased by 300 °C, which led to little volatilisation of the sealing phase. Further, the mass ablation ratio of the above coating was 3.19 × 10^?4 g/s, decreasing 31% compared to that of a ZrB₂/SiC coating. The formed dense surface structure of the coatings showed considerable oxygen obstructive effects. These findings indicate that the modified coatings show considerable anti-ablation performance, which provides effective anti-ablation protection for the C/C composite substrate.     

Preparation of Porous Al2O3-Ceramics by Biotemplating of Wood

A new approach for preparing of microcellular ceramic materials is the reproduction of wood morphologies by biotemplating, where the structural features of the native wood are maintained in the ceramic product. Biomorphic Al₂O₃-ceramics were manufactured via the sol-gel route by repeated infiltration of low viscous alumina sols into wood preforms and subsequently sintered in air at 1550°C. The microstructure and phase formation during processing were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), density and porosimetry measurements. In contrast to conventional processed, highly-porous Al₂O₃-ceramics, the microstructure of the biomorphic Al₂O₃-ceramics is characterized by an uniaxial pore morphology with pore diameters in the micrometer range, depending on the initially used wood template.